CN1268009C - 含光辐射元素的光源 - Google Patents

含光辐射元素的光源 Download PDF

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Publication number
CN1268009C
CN1268009C CNB018214673A CN01821467A CN1268009C CN 1268009 C CN1268009 C CN 1268009C CN B018214673 A CNB018214673 A CN B018214673A CN 01821467 A CN01821467 A CN 01821467A CN 1268009 C CN1268009 C CN 1268009C
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China
Prior art keywords
light source
luminous element
led
radiation
light
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Expired - Lifetime
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CNB018214673A
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CN1483224A (zh
Inventor
斯特凡·塔什
彼得·帕克勒
贡杜拉·罗特
瓦尔特·特夫斯
沃尔夫冈·肯普弗特
德特勒夫·斯塔里克
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Tridonic Optoelectronics GmbH
Toyoda Gosei Co Ltd
Original Assignee
Tridonic Optoelectronics GmbH
Leuchtstoffwerk Breitungen GmbH
Litec GbR
Toyoda Gosei Co Ltd
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Application filed by Tridonic Optoelectronics GmbH, Leuchtstoffwerk Breitungen GmbH, Litec GbR, Toyoda Gosei Co Ltd filed Critical Tridonic Optoelectronics GmbH
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    • 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
    • C09K11/7783—Luminescent, 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
    • C09K11/7795—Phosphates
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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Abstract

本发明涉及一光源，其包含光辐射元素，该光辐射元素可在第一光谱区发生辐射，光源还含一发光体，该发光体来源于碱土正硅酸盐族，吸收光源发射的一部分光并在另一光谱区发生辐射。按照本发明，该发光体是由二价铕激活的活性碱土金属正硅酸盐，成分为：(2-x-y)SrO·x(Ba，Ca)O·(1-a-b-c-d)SiO2·aP2O5·bAl2O3·cB2O3·dGeO2:yEu2+和/或(2.x.y)BaO·x(Sr，Ca)O·(1-a-b-c-d)SiO2·aP2O5bAl2O3·cB2O3·dGeO2:yEu2+。采用该发光体可很好地对所希望的颜色(色温)进行调整。该光源还可含有一其它的选自碱土金属铝酸盐族的由二价铕和/或锰基团激活的发光体，和/或一其它选自于族Y(V，P，Si)O4:Eu或碱土-镁-二硅酸盐的发射红光的发光体。

Description

含光辐射元素的光源
技术领域
本发明涉及一可产生白光的光源，包括一可辐射蓝和/或紫外射线的光-辐射-二极管(LED)，并至少含有一发光体，其可在另一光谱区辐射部分蓝和/或紫外射线和本身的射线。
背景技术
无机LED主要表现为寿命长，占地小，对震动不敏感和光谱窄带辐射。
丰富的辐射色——特别是宽带光谱——无法借助LED中的活性半导体物质的内在辐射而实现或仅能无效地实现。其特别适合于产生白光。
在WO 00/33390中给出了一种光辐射的仪器，其包括一与发光材料混合物一同作用的仅辐射蓝光的LED或激光二极管。将一光谱区处于420nm至470nm辐射的LED与一得自至少两种发光材料的发光材料混合物组合，以产生白色的光。这两种必需的发光材料必须可辐射不同的光谱。所应用的发光材料混合物总是包括一红组分和一绿组分。借助与LED发出的蓝射线的色混合可产生白光。
根据现有技术，将借助色泽变换生成半导体本身无法实现的辐射色。
大多数的色泽转换技术均是基于这一原理，即至少在LED上安排了一种发光体。其吸收了部分发射辐射，并由此被激励为光致发光。该辐射或光源色会产生其传输射线和发光材料辐射射线的混合。
作为发光体原则上既可采用有机的，也可采用无机的体系。与有机体系相比无机色素的主要优点是具有高的化学，温度和辐射稳定性。与无机LED的长寿命相关，长寿命的无机发光体保证了得自两种成分的光源的高的色位稳定性。
要想将由辐射蓝光的LED发出的辐射被转换成白光，就需要发光材料，其可完全吸收蓝光(450-490nm)，并高效地将其绝大部分转换为黄色发光射线。然而仅有极少数无机发光体可满足这一要求。目前大多数用作对于蓝色LED的色泽转换色素的材料来自YAG-发光材料族(WO 98/05078；WO98/05078；WO98/12757)。这当然就有一个缺点，其仅在小于560nm具有最大辐射时才具有足够高的效率。基于该原因采用YAG-色素结合蓝色二极管(450-490nm)仅可实现色温6000至8000K且色归还相对较低(色还原指数Ra的典型值处于70至75之间)的冷-白的光色。因此大大限制了应用的可能性。首先在白光源作为普通照明应用时，通常要求发光剂的色归还质量较高；另外消费者，特别是在欧洲和北美的消费者偏爱色温处于2700至5000K间的较暖光色。
对WO 00/33389来说采用Ba2SiO4∶Eu2+作为转换蓝光LED的发光体。发光材料Ba2SiO4∶Eu2+的最大辐射处于约505nm，因此采用这样的组合保证不能产生白光。
在S.H.M.Poort等人的论文“Optical properties of Eu2+-activatedorthosilicates and orthophospates”，Journal of Alloys and Compounds260(1997)，S 93-97中对Eu-活性的Ba2SiO4以及磷酸盐如KBaPO4和KSrPO4的特性进行了研究。其中还确认了Ba2SiO4的辐射处于约505nm。
发明内容
本发明的任务是提供一改良的采用光-辐射-二极管(LED)作为射线源的光源，这里该射线源可在UV-区或蓝色区(370至490nm)发生辐射，通过采用一种改良的发光材料，使得可以产生出较高效的白色光，第一次使得将该白光源用于照明的用途成为可能。
同时避免了现有技术已知的缺点。另外使得可对一种或多种发光材料的色温在一较大区域内进行调整成为可能，以满足用户不同的要求，特别是对色位进行的调整的要求，其色位应处于普通照明所确定的耐受椭圆(Toleranzellipsen)CIE之内。
按照本发明该任务将通过一开头所述的光源来解决，
●该发光体是由二价铕激活的具有下述组成的碱土金属正硅酸盐或由此组成的混合物：
(a)(2-x-y)SrO·x(Bau，Cav)O·(1-a-b-c-d)SiO2·aP2O5bAl2O3cB2O3dGeO2∶y Eu2+
其中
0≤x＜1.6             0.005＜y＜0.5      x+y≤1.6
0≤a，b，c，d＜0.5    u+v＝1
(b)(2-x-y)BaO·x(Sru，Cav)O·(1-a-b-c-d)SiO2·aP2O5bAl2O3cB2O3dGeO2∶y Eu2+。
其中
0.01＜x＜1.6          0.005＜y＜0.5
0≤a，b，c，d＜0.5    u+v＝1             x·u≥0.4
●该发光体在黄-绿，黄或橙色光谱区辐射射线；
●通过在所述区域内选择参数，可以对所产生出的白色光的色温和常规色指数进行调节。
在一优选实施例中，a，b，c和d中至少有一个值大于0.01。另外在上述的发光体中的一部分硅可被镓替代。
惊奇地发现，具有良好色归还和较高光收益的白光可通过将一蓝色LED和一发光体化合来实现，该发光体选自于按照本发明上述组份的铕激活的碱土金属正硅酸盐族。与基于纯钯正硅酸盐和可辐射出蓝-绿色光的发光体不同，通过钯-锶-正硅酸盐混合结晶可产生出黄-绿，黄至黄-橙色，以及通过将钙置入正硅酸盐晶格甚至可以产生稳定的橙色发光，因此通过将蓝色LED的传输光与所选发光体的辐射光混合可产生较高色归还和较高效率的白光。已知的通过在正硅酸盐上用Sr取代Ba产生的辐射色位移至今为止仅是用于上述Poort等人文章的强UV-辐射(254nm-激励)激励；该现象在用于440-475nm范围的蓝光辐射时会令人惊异地加强，然而尚未对此有记载。至今为止采用长波UV-辐射或蓝光激励的Ba-Sr-Ca-正硅酸盐混合结晶及其强烈的辐射能力还是未知的。
所选择的发光体也可与同族的其他发光体和/或与另外的不属于同族的发光材料混合使用。上述的发光材料属于例如蓝光辐射的由二价铕和/或锰激活的碱土金属铝酸盐，以及红辐射的来自族Y(V，P，Si)O4∶Eu，Bi，Y2O2S∶Eu，Bi的发光体或具有分子式Me(3-x-y)MgSi2O8∶xEu，YMn的铕-和锰激活的碱土-镁-二硅酸盐：Eu2+，Mn2+，其中
0.005＜x＜0.5
0.005＜y＜0.5
和Me＝Ba和/或Sr和/或Ca。
如在下述的实施例中说明的，在按照本发明的混合-结晶-发光体中的Sr-部分不允许太低，以使其可产生白光。
令人惊奇的是进一步发现，在正硅酸盐晶格中P2O5，Al2O3和/或B2O3的附加置入以及一部分硅被锗的取代同样对每一发光体的发射光谱具有显著影响，因此它可以对于实际应用而进一步作出有益的改动。此外小离子如Si(IV)通常引起长波区域中最大辐射的位移，而大离子会将辐射的中心向短波长方向移动。另外还表明，当在发光晶格中另外混合少量的一价离子如卤化物和/或碱金属离子，对本发明发光体的结晶性、辐射能和稳定性是有益的。
按照本发明进一步有益的安排，该光源至少含有两种不同的发光体，其中至少有一个是碱土金属正硅酸盐发光材料。以这种方式，该按照各用途所需的白色可被精细地加以调节，特别是其Ra-值可达到大于80。本发明的另一有益的变体是一在紫外光谱区的化合物，例如在370至390nm间的区域，辐射的LED具有至少三种发光材料，其中至少有一种是按照本发明的碱土金属正硅酸盐发光材料。作为在相应的发光材料混合物中添加的发光材料可使用辐射蓝光的碱土金属铝酸盐，其由含铕和/或锰和/或得自Y(V，P，Si)O4∶Eu，Bi，Y2O2S∶Eu，Bi族或铕-和锰的碱土金属-锰-二硅酸盐族的辐射红光的发光体激活。
按照本发明的光源的机械实施存在多种方法。按照其中一种实施方法是将一或多个LED-片排列在一反射器内的护板上，并把发光体分散放入反射器上的光片中。
也可以将一个或LED-片排列在一反射器内的护板上，并把发光体涂在反射器上。
优选地，将LED-片和一透明圆弧形的铸件浇注在一起。该铸件一方面起着机械保护作用，另一方面还可改善光学的特性(使LED-块有较好的光线透出)。
该发光体也可被分散于一铸件内，该铸件与置于护板上的LED-片和聚合物透镜间应尽可能无间隙地结合，其中聚合物透镜和铸件折射率差别最大为0.1。该铸件既可直接连接LED-块，也可与一透明铸件浇注在一起(这样就有一透明的铸件和一具发光体的铸件)。由于折射率近乎相同，在光滑的表面上几乎不存在反射损失。
特别是该聚合物透镜为一球或椭球状中空，该中空可用铸件填充，以使得LED-阵列固定于与聚合物透镜间距离极小的地方。由此可减小机械装配的高度。
为达到发光体的均匀分布，实际应用中最好将发光体悬浮在无机基质液中。
对采用至少两种发光体而言，当至少两种发光体单独在基质液中分散时，将它们在光扩散方向上前后排列是有益的。以这样的方式，与不同发光体的统一分散相比可降低发光体的浓度。
下面是在本发明优选实施例中制造发光体的主要步骤：
对于碱土金属正硅酸盐-发光体的制造，将相应所选择的按照化学计量法所得量的原料碱土金属碳酸盐，二氧化硅以及氧化铕组份密切混合，在一发光材料的制备中常见的晶体反应中，在温度1100℃至1400℃下减压使其转换为所希望的发光体。同时，为有利于结晶性，应向反应混合物中添加少量，特别是应该小于0.2Mol，的氯化铵或其他卤素。本发明中还可使用锗，硼，铝，磷替代部分的硅，所述的这些可在氧中热作用下分解的元素可通过添加相应量的化合物来实现。通过将少量的碱金属离子置入各晶格也可达到类似的效果。
按照本发明所获得的正硅酸盐发光体在波长510至600nm间发生辐射，具有在110nm之内的半值宽。
通过适当的设置反应参数和特定的添加物，如一价卤素-和/或碱金属，可使得按照本发明的发光体的颗粒大小分布最佳地满足各应用的需要，从而不再需要有害的机械破碎处理。因此所有窄和宽带的颗粒大小分布可在平均颗粒大小d50在约2μm至20μm间调整。
附图说明
本发明的其它优点将在下述的实施例和附图阐述。
图1-6显示了不同的根据本发明的LED光源的光谱图(依赖于波长的相对强度I)；图7-10显示了根据本发明的LED光源的不同实施方式。
最佳实施方式
图1给出了一具色温2700K的白色LED的辐射光谱图，其是由在第一光谱区具有中心波长464nm辐射蓝光的LED和一按照本发明具有成分(Sr1，4Ca0，6SiO4∶Eu2+)在第二光谱区具有最大596nm辐射的发光体的组合物产生的。
另一对于在464nm辐射的LED与按照本发明的正硅酸盐发光体的组合物例子如图2和3所示。如果采用一辐射黄色的具有成分Sr1，90Ba0，08Ca0，02SiO4∶Eu2+的发光体作为色转换，可校准出一具有色温4100K的白光色，而此时若采用例如发光体Sr1，84Ba0，16SiO4∶Eu2+，仅可获得一色温6500K的白光源。
图4给出了一464nm-LED和两种按照本发明的正硅酸盐发光体的组合物的典型光谱。该所采用的发光材料具有组成Sr1，4Ca0，6SiO4∶Eu2+和Sr1，00Ba1，00SiO4∶Eu2+。对在图4中所给出的具体光谱图而言，其具有色温5088K和色回归指数Ra 82。虽然在所选择发光体数量关系相关性中，所有的色温均可在在区域约3500K至7500K间实现，但这里来自两种按照本发明的碱土金属正硅酸盐-发光体的如此混合首先具有一大优点，即Ra-值均可大于80。
在图5中举例作了说明。该生成的光谱得自一464nm-LED和一来自两种发光体Sr1，6Ca0，4Si0,98Ga0,02O4∶Eu2+和Sr1，10Ba0，90SiO4∶Eu2+的一混合物的组合物，在色温5000K时Ra-值为82。
如果采用在第一光谱区具有最大370nm-390nm辐射的UV-LED作为射线辐射的元素，则通过该LED和一按照本发明图4的发光体与一定量蓝-绿辐射的钡-镁-铝酸盐发光材料：Eu，Mn的发光材料混合的组合，可实现Ra-值大于90。图6给出了一相应白光源的辐射光谱图，其在色温6500K时Ra值为91。
其它的实例得出下述的清单。此外除所采用的无机LED辐射波长和各按照本发明的发光体组成外，还给出了所得出的色温和Ra-值以及光源的色位：
T＝2778K(464nm+Sr1，4Ca0，6SiO4∶Eu2+)；x＝0.4619，y＝0.4247，Ra＝72
T＝2950K(464nm+Sr1，4Ca0，6SiO4∶Eu2+)；x＝0.4380，y＝0.4004，Ra＝73
T＝3497K(464nm+Sr1，6Ba0，4SiO4∶Eu2+)；x＝0.4086，y＝0.3996，Ra＝74
T＝4183K(464nm+Sr1，9Ba0，08Ca0，02SiO4∶Eu2+)；x＝0.3762，y＝0.3873，Ra＝75
T＝6624K(464nm+Sr1，9Ba0，02Ca0，08SiO4∶Eu2+)；x＝0.3101，y＝0.3306，Ra＝76
T＝6385K(464nm+Sr1，6Ca0，4SiO4∶Eu2++Sr0，4Ba1，6SiO4∶Eu2+)；x＝0.3135，y＝0.3397，Ra＝82
T＝4216K(464nm+Sr1，9Ba0，08Ca0，02SiO4∶Eu2+)；x＝0.3710，y＝0.3696，Ra＝82
3954K(464nm+Sr1，6Ba0，4SiO4∶Eu2++Sr0，4Ba1，6SiO4∶Eu2++YVO4∶Eu3+)；x＝0.3756，y＝0.3816，Ra＝84
T＝6489K(UV-LED+Sr1，6Ca0，4SiO4:Eu2++Sr0，4Ba1，6SiO4∶Eu2++钡-镁-铝酸盐：Eu2+)；x＝0.3115，y＝0.3390，Ra＝86
T＝5097K(464nm+Sr1，6Ba0，4(Si0，98B0.02)O4∶Eu2++Sr0，6Ba1，4SiO4∶Eu2+)；x＝0.3423，y＝0.3485，Ra＝82
T＝5084K  (UV-LED  +Sr1，6Ca0，4(Si0,99B0,01)O4∶Eu2++Sr0，6Ba1，4SiO4∶Eu2++锶-镁-铝酸盐：Eu2+)；x＝0.3430，y＝0.3531，Ra＝83
T＝3369K(464nm+Sr1，4Ca0，6Si0，95Ge0,05O4∶Eu2+)；x＝0.4134，y＝0.3959，Ra＝74
T＝2787K(464nm+Sr1，4Ca0，6Si0，98P0,02O4,01∶Eu2+)；x＝0.4630，y＝0.4280，Ra＝72
T＝2913K(464nm+Sr1，4Ca0，6Si0，98Al0,02O4∶Eu2+)；x＝0.4425，y＝0.4050，Ra＝73
T＝4201K
在本发明的一个优选实施方式中以下述方式进行色转换；
将一个或多个LED-片1(见图7)固定在一护板2上。将胶囊包3以半球形或半椭圆形直接布置在LEDs上(一方面保护LED-片，另一方面使得在LED-片中产生的光可以更好地耦合出来)。该胶囊包3既可包裹每一单个LED，也可将所有LED包在一起。可将如此装备的护板2放入反射器4中，即将其盖在LED-片1上。
在反射器4上放置一光板5。其一方面起着保护排布次序的作用，另一方面在该光板中混入了发光体6。通过光板5的蓝光(或紫外射线)将在通过时部分地借助发光体6转换至第二光谱区，并由此在总体上获得白颜色的感觉。导波作用同平行平面片中产生的一样，导波作用引起的损耗可借助板的不透明、散射的特性来减少。另外反射器4仅允许预备好的光传到光板5上，这样就立即减少了总的反射作用。
还可以将发光体6涂到反射器4上，如图8所示。这时就不再需要光板了。
还可将一反射器4’设置在每个LED-片1上(见图9)，并将其浇铸为圆弧形状(胶囊包3’)，在每一反射器3’上，即总的布局上面设置一光板5。
对照明源的生产而言，较实用的是应用单个-LED的LED-阵。在本发明方法的一个实施方式中，在一LED-片1直接固定在护板2上的LED-阵1’(见图10)上的色转换是以下述形式来进行：
借助铸件3(例如环氧化物)将一LED-阵1’(见图10)与一另一材质(例如PMMA)的透明聚合物透镜7相粘结。聚合物透镜7和铸件3的材质按照尽可能近似的折射值来选择——即相适合。该铸件3处于聚合物透镜7的最大球型或椭圆型的空洞中。空洞的形状具有这样的作用：因为在铸件3中分散有色转换材料，因此借助造型确保辐射色泽与角度无关。还可以首先将阵与一透明的铸件铸在一起，然后将聚合物透镜粘在含有色转换材料的铸件的连接介质上。
对于生产具有极佳色回归且其中至少含有两种不同发光体的白色LEDs，不在一种基质液中一起分散，而是分别分散和涂布是有益的。这特别适合于那种通过多级色转换过程得到最终光色的组合物。也就是说，借助一辐射过程来产生最单调的辐射色，如下所述：通过第一发光体的LED-辐射的吸收-第一发光体的辐射-通过第二发光体的第一发光体的辐射的吸收和第二发光体的辐射。特别是对这样的过程而言，优选地将单个的材料前后置于光扩散方向上，因为与统一将不同材料进行分散相比，可降低材料的浓度。
本发明并不仅限于给出的实例。发光体也可引入到聚合物透镜中(或其它透镜)。也可将发光体直接设置在LED-块或透明的铸件表面上。还可将发光体与撒用粒一起加入到基质液中。由此可避免基质液的沉降，以保证均匀的透光。

Claims (15)

1.可产生白光的光源，包括一用于辐射蓝和/或紫外射线的光-辐射-二极管(LED)，并至少含有一发光体，其可吸收部分蓝和/或紫外射线并在另一光谱区辐射本身的射线，其特征是
●该发光体是由二价铕激活的具有下述组成的碱土金属正硅酸盐或由此组成的混合物：
a)(2-x-y)SrO·x(Bau，Cav)O·(l-a-b-c-d)SiO2·aP2O5·bAl2O3·cB2O3·dGeO2:yEu2+
这里
0≤x＜1.6             0.005＜y＜0.5      x+y≤1.6
0≤a，b，c，d＜0.5    u+v＝1
b)(2-x-y)BaO·x(Sru，Cav)O·(l-a-b-c-d)SiO2·aP2O5·bAl2O3·cB2O3·dGeO2:yEu2+。
这里
0.01＜x＜1.6          0.005＜y＜0.5
0≤a，b，c，d＜0.5    u+v＝1             x·u≥0.4
●该发光体在黄-绿，黄或橙色光谱区辐射射线；
●通过在所述区域内选择参数，可以对所产生出的白色光的色温和常规色指数进行调节。
2.按照权利要求1的光源，其特征是a，b，c和d中至少一个值大于0.01。
3.按照权利要求1或2的光源，其特征是发光体中的一部分硅被镓离子替代。
4.按照权利要求1或2的光源，其特征是含有另外的来自碱土铝酸盐族，由二价铕和/或锰激活的发光体，和/或另外的来自组Y(V，P，Si)O4:Eu，Bi、或者Y2O2S:Eu，Bi、或Eu2+，Mn2+的碱土-镁-二硅酸盐的红辐射发光体，所述的硅酸盐具有分子式Me(3-x-y)MgSi2O8:xEu，yMn，其中
0.005＜x＜0.5
0.005＜y＜0.5
和Me＝Ba和/或Sr和/或Ca。
5.按照权利要求1或2的光源，其特征是在发光体晶格中置入一价离子。
6.按照权利要求5的光源，其特征是所述的一价离子是卤化物和/或碱金属。
7.按照权利要求1或2的光源，其特征是该LED在一300至500nm间的光谱区内辐射，该发光体在一430至650nm间的光谱区内辐射，该光源发出色回归指数Ra＞70的白色光。
8.按照权利要求1或2的光源，其特征是将一或多个LED-片(1)布置在一反射器(4)内的护板(2)上，并把发光体(6)分散入装置在反射器(4)上的光板(5)中。
9.按照权利要求1或2的光源，其特征是将一或多个LED-片(1)布置在一反射器(4)内的护板(2)上，并把发光体(6)涂在反射器(4)上。
10.按照权利要求8或9的光源，其特征是将LED-片(1)与透明的圆弧形的铸件(3，3’)浇铸在一起。
11.按照权利要求1或2的光源，其特征是发光体分散于一铸件中(3)，该铸件与置于护板(2)上LED-片(1)的安排(1’)和聚合物透镜(7)间应无实体空间，这里聚合物透镜(7)和铸件(3)的折射率差最大为0.1。
12.按照权利要求10的光源，其特征是该聚合物透镜(7)为一球或椭圆型中空形状，该中空可用铸件(3)填充，以使得LED-安排(1’)与聚合物透镜(7)间的距离极小。
13.按照权利要求1或2的光源，其特征是将发光体悬浮在无机的基质液中。
14.按照权利要求1或2的光源，其特征是至少两种发光体单独在基质液中分散，并将它们在光扩散方向上前后排布。
15.按照权利要求1或2的光源，其特征是发光体体积分布的平均颗粒大小d50处于2μm至20μm间。
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WO2002054503A1 (fr) 2002-07-11
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US20040051111A1 (en) 2004-03-18
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US20050082574A1 (en) 2005-04-21
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CN1291503C (zh) 2006-12-20
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ATE465518T1 (de) 2010-05-15
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