CN1269233C - 宽光谱含铽石榴石磷光体及其结合构成的白色光源 - Google Patents
宽光谱含铽石榴石磷光体及其结合构成的白色光源 Download PDFInfo
- Publication number
- CN1269233C CN1269233C CNB028110412A CN02811041A CN1269233C CN 1269233 C CN1269233 C CN 1269233C CN B028110412 A CNB028110412 A CN B028110412A CN 02811041 A CN02811041 A CN 02811041A CN 1269233 C CN1269233 C CN 1269233C
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- rare earth
- phosphor
- terbium
- light
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 39
- 230000005855 radiation Effects 0.000 claims abstract description 21
- -1 rare earth-activated terbium Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 62
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Classifications
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/7774—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/7783—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
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
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- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
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- H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
- H01L2224/491—Disposition
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Abstract
稀土元素活化的含铽石榴石磷光体能够吸收范围从近紫外光到蓝色光的辐射,并发射范围从490纳米到770纳米的可见光的宽光谱。磷光体的光发射在450纳米下激发时存在一个在人眼最大敏感度范围内的峰值。结合紫外/蓝色光发光二极管和这一磷光体的光源,能够提供符合或接近普朗克曲线的白色光,因而可以用于普通照明。
Description
与本发明相关的背景技术
本发明涉及发射宽光谱可见光的磷光体,它具有用稀土金属离子活化的石榴石结构。特别是,本发明涉及用铈活化的铽铝氧化物石榴石磷光体,它在蓝色光激发下发射黄色光。本发明还涉及使用这些磷光体的白色光源。
磷光体是发冷光材料,它在电磁光谱的一区域吸收辐射能而在电磁光谱的另一区域发射能量。磷光体一个重要类别的磷光体是化学纯度非常高并且具有受控成分的结晶无机化合物,其中加入少量的其它元素(称为“活化剂”),使其转化为有效的荧光材料。采用活化剂和无机化合物适当的组合,可以控制发射光的颜色。最有用和熟知的磷光体,响应可见区之外的电磁辐射的激发,发射在电磁光谱可见部分的辐射。熟知的磷光体已经用于汞蒸汽放电灯中,以将激发的汞蒸汽发射的紫外(“UV”)辐射转化成可见光。其它磷光体在被电子(用于阴极射线管)或X射线(例如,在X射线探测系统中的闪烁体)激发后,能够发射可见光。
使用磷光体的照明设备的效率随着激发辐射的波长与发射辐射的波长之间的差别变窄而增加。因此,在寻求改善白色光源的效率时,努力致力于发现具有波长长于紫外辐射的激励辐射源以及响应该波长的磷光体。近期,发光二极管(“LED”)技术的进步,已经带来在近紫外到蓝色光范围中发射的高效能的发光二极管。这里使用的术语“近紫外”表示具有波长范围从约315纳米到约400纳米的紫外辐射。这些在近紫外到蓝色光范围中发射辐射的发光二极管将在下文中称为“紫外/蓝色光发光二极管”。如本文所使用的,紫外/蓝色光发光二极管可以发射具有波长在近紫外范围、在蓝色光范围、或在从近紫外到蓝色光的宽范围中的辐射。提供一定范围的磷光体,其可为这些紫外/蓝色光发光二极管辐射源发射的辐射所激励,以便于灵活地应用磷光体来产生各种颜色的发光二极管,此将是照明技术的一个进步。当这种磷光体与来自紫外/蓝色光发光二极管的发射结合时,可提供消耗很少能量的有效且耐久的照明装置。
近来出现了许多基于铟、铝、和镓的氮化物组合的近紫外/蓝色光发光二极管。例如,美国专利5,777,350披露了包括多层铟和镓氮化物以及p和n型AlGaN的发光二极管,其发射波长范围是约380纳米到约420纳米。这种发光二极管的活性层可以掺杂其它材料以移动发光二极管在紫外/蓝色光波长范围内的发射峰。在蓝色光波长具有发射峰的发光二极管,与用铈活化的发黄色光的钇(yittium)铝石榴石磷光体(“YAG:Ce”)涂层结合,以产生白色光,于美国专利5,998,925中有披露。尽管对白色光设备需要的相当大的部分可以由基于发光二极管的装置来满足,但紫外/蓝色光发光二极管与磷光体的结合能力受到限制,因为YAG:Ce是仅知的可由在蓝色光范围的辐射所激发的发射黄色光的磷光体。
因此,我们有必要提供在近紫外/蓝色光范围可激发并在可见光谱区发射的新的磷光体。我们还希望提供在从蓝绿色到红色的宽波长范围内发射光的新颖的磷光体,从而它们可与紫外/蓝色光发光二极管结合以产生高效率和/或高显色指标(“CRI”)的白色光。
发明简述
本发明提供磷光体,这些磷光体可被具有波长在近紫外/蓝色光范围(从约315纳米到约480纳米)的辐射所激发,从而在从约490纳米到约770纳米的宽波长范围内高效发射可见光,在绿色到黄色波长范围内具有一个发射峰。一般地,本发明的磷光体是固体氧化物,其至少含有铽和至少含有一种元素,该元素选自包括铝、镓、和铟的组;并且可被至少一种稀土金属离子活化,该稀土金属离子选自由铈、镨、钕、钐、铕、钆、镝、钬、铒、铥、镱、和镥组成的组。铽可以部分地由至少一种稀土金属取代,选自由钇、镧、钆、钐、和镥组成的组。本发明的磷光体具有石榴石结构和通式
(Tb1-x-yAxREy)3DzO12
其中A是一种选自由Y、La、Gd、和Sm组成的组的成分;
RE是一种选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、
Tm、Yb、Lu、及其组合组成的组的成分;D是一种选自由Al、
Ga、In、及其组合组成的组的成分;x的范围是从0到约0.5,y
的范围是从约0.0005到约0.2,而z的范围是从约4到5。在本
发明的一个方面中,4<z<5。
根据本发明的另一方面,提供了制造稀土活化含铽石榴石磷光体的方法,包括以下步骤:(1)提供化学计算量的铽的含氧化合物,至少一种稀土金属的含氧化合物,该稀土金属选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、和Lu组成的组;和至少一种成分的含氧化合物选自由Al、Ga、和In组成的组;(2)将含氧化合物共同混合以形成混合物;(3)在混合物中可选择地加入至少一种助熔化合物(fluxing compound),选自由Tb、Al、Ga、In、Y、La、Gd、Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、和Lu的氟化物组成的组,其量足以起到助熔剂的作用;以及(4)在还原气氛下于某一温度烧制混合物足够的时间,使混合物转化成稀土活化含铽石榴石磷光体。
在本发明的另一方面,化学计算量的铽的含氧化合物溶液;至少一种其它稀土金属,选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、和Lu组成的组;以及至少一种金属,选自由Al、Ga、和In组成的组,在碱性溶液中沉淀以得到金属氢氧化物的混合物。沉淀氢氧化物的混合物在氧化气氛中煅烧。经煅烧的材料进一步彻底混合,然后在还原气氛下于某一温度烧制足够的时间,使经煅烧的混合物转化成稀土活化含铽石榴石磷光体。
在本发明的又一方面,提供了发射白色光的光源,该光源包括紫外/蓝色光发光二极管,一定数量的稀土活化含铽石榴石磷光体,其通式为(Tb1-x-yAxREy)3DzO12,其中A、RE、D、x、y、和z如上文所定义。磷光体接近紫外/蓝色光发光二极管放置,以便磷光体至少部分吸收紫外/蓝色光发光二极管发射的辐射,并转换可见光。磷光体发射的光和紫外/蓝色光发光二极管发射的部分辐射结合在一起产白色光。
附图简要说明
图1表示本发明的具有组成为(Tb0.97Ce0.03)3Al4.9O12的磷光体室温激发光谱。
图2表示(Tb0.97Ce0.03)3Al4.9O12磷光体的室温发射光谱。
图3表示使用本发明的磷光体的白色光源的一个具体实施例。
图4表示紫外/蓝色光发光二极管和本发明含铽磷光体结合制造光源范围的色坐标。
发明详述
本发明提供一种磷光体,它可有效地被具有近紫外到蓝色范围波长的辐射激发,并有效地发射具有从蓝色到红色(从约490纳米到约770纳米)的宽光谱的可见区的光。该磷光体在绿色到黄色范围(从约540纳米到约600纳米)中具有一个发射峰,其包括了人眼的最大敏感范围。本发明的磷光体是稀土活化含铽石榴石,具有通式(Tb1-x-yAxREy)3DzO12(在下文中也称作“TAG:Ce”),其中A是一种选自由Y、La、Gd、和Sm组成的组的成分;RE是一种选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、和Lu组成的组的成分;D是一种选自由Al、Ga、和In组成的组的成分;x的范围是从0到约0.5,较好是从0到约0.3,优选是从0到约0.2;y的范围是从约0.0005到约0.2,较好是从约0.005到约0.1,优选是从约0.005到约0.07;而z的范围是从约4到约5,较好是从约4.5到5,优选是从约4.6到小于约5。
在一个优选的具体实施例中,磷光体是用铈活化的铽铝石榴石,具有通式(Tb1-yCey)aAl4.9O12,这里y的取值如上述定义,而a的范围是从约2.8到3。
在另一个优选的具体实施例中,铝部分地由镓、铟、或其组合取代。在此情况下,磷光体具有通式(Tb1-yCey)3(Al1-r-sGarIns)zO12,其中y和z的定义如上所述,同时当0<s≤0.5和r+s<1时,0≤r≤0.5,或当0≤s≤0.5和r+s<1时,0<r≤0.5。较好地,r的范围是从约0.005到约0.3而更好地是从约0.05到约0.2;同时较好地,s的范围是从约0.005到约0.3而更好地是从约0.05到约0.2。
在另一个优选的具体实施例中,铽部分地被Y、Gd、Sm之一,或其组合取代,而铝未被取代。在这种情况下,磷光体具有的通式是(Tb1-y-u-v-wCeyYuGdvSmw)3AlzO12,其中y和z的定义如上所述,0≤u、v、w≤0.5,同时0.0005≤y+u+v+w<1。较好地每个u、v、和w的范围是从约0.005到约0.3而更好地是从约0.005到约0.1。
在另一个优选的具体实施例中,磷光体所具有的通式是(Tb1-x-yAxCey)3AlzO12,其中A是Y或Gd,0<x≤0.5,而y和z的定义如上所述。
本发明的磷光体的制造方法包括以下步骤:(1)提供化学计算量的铽的含氧化合物;至少一种稀土金属的含氧化合物,该稀土金属选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、和Lu组成的组;以及至少一种成分的含氧化合物,该成分选自由Al、Ga、和In组成的组;(2)将含氧化合物共同混合以形成混合物;以及(3)在还原气氛下于某一温度烧制混合物足够的时间,使混合物转化成稀土活化含铽石榴石磷光体。
在本发明的另一方面,一定数量的至少一种金属的氟化物,该金属选自由铽、铝、镓、和铟组成的组,作为助熔剂在混合步骤之前或期间加入到含氧化合物的混合物之中。氟化合物的量占混合物总重量的百分数少于约20,优选少于约10,对于熔合目的是适当的。
含氧化合物可用任何机械方法共同混合,包括但不限于,在高速混合器或螺带式混合器中搅拌或混合。这些含氧化合物可在球磨机、锤磨机、或喷射磨中结合并研磨成粉。特别是当为了后续的沉淀将含氧化合物的混合物制成溶液时,该混合可通过湿磨进行。如果混合物是湿的,它可在被烧制之前首先干燥,烧制在还原气氛下于从约900℃到约1700℃的温度下进行,较好是从约1000℃到约1600℃,更好是从约1200℃到约1500℃,烧制时间要足以将所有的混合物转化成最终的石榴石成分。烧制可以采用分批或连续工艺进行,优选采用搅拌或混合作用以促进良好的气-固接触。烧制时间取决于被烧制的混合物的量、通过烧制设备的气体传导速率、以及在烧制设备中气-固接触的质量。典型地,多达约10小时的烧制时间是适当的。还原气氛一般包括还原性气体例如氢气、一氧化碳、或其组合,并且可选地用惰性气体稀释,如氮气、氦气、氖气、氩气、氪气、氙气、或其组合。可替换地,含有混合物的坩埚可以包装在含有高纯度碳颗粒的第二个封闭的坩埚中,并在空气中烧制,以便碳颗粒与存在于空气中的氧气反应,从而,产生所需的一氧化碳来提供还原气氛。
实施例
下述量的铽、铈、和铝的氧化物与氟化铝进行充分的干燥混合。
Tb4O7 :6.805g
CeO2 :0.194g
Al2O3 :3.062g
AlF3 :0.105g
这一混合物放入第一个坩埚中,此坩埚放在第二个封闭的坩埚内部,其中含有用混合物包装的椰子炭颗粒,而放在一起的混合物在1450℃下烧制5小时,烧制是在箱式炉中在还原气氛下进行,该还原气氛是在氮气中的10%(体积)的H2和通过椰子炭的反应所产生的气体的结合。在5小时结束后,固体在同样的H2/N2混合物气流下冷却。最终的磷光体具有组成为(Tb0.97Ce0.03)3Al4.9O12,如通过元素分析所确定的。对磷光体在450纳米激发下的激发光谱和发射光谱进行了测量并分别表示在图1和图2中。本发明的磷光体在从约490纳米到约770纳米的可见区表现出宽发射光谱。因此,发射覆盖了从蓝绿色到红色光的范围。所以,这一发射光谱与,例如,发射蓝色光发光二极管所发射的蓝色光的结合,应当提供白色光。
用于磷光体合成的一种或多种原材料可以是不同于氧化物的含氧化合物,例如硝酸盐、硫酸盐、醋酸盐、柠檬酸盐、或氯酸盐。例如,一定数量的Tb4O7、Al(NO3)3·9H2O、Ce(NO3)3·6H2O和AlF3混合并溶于硝酸溶液中。选择酸溶液的强度以迅速溶解含氧化合物,而该选择是本领域技术人员应知的。然后在搅拌下向含有Tb、Ce、和Al的酸性溶液中加入过量的氢氧化铵,以沉淀出Tb、Ce、和Al的氢氧化物的混合物。有机碱,例如甲醇胺、乙醇胺、丙醇胺、二甲醇胺、二乙醇胺、二丙醇胺、三甲醇胺、三乙醇胺、或三丙醇胺,可以用来代替氢氧化铵。过滤沉淀物,用去离子水洗涤,然后干燥。球磨干燥的沉淀物或用其它方法彻底混合,然后在空气中于约400℃到约1600℃下煅烧足够的时间,以确保原材料基本上完全脱水。煅烧过程可在恒温下进行。可替换地,在煅烧持续时间内,煅烧温度可以从周围环境温度升温到(ramped)并保持在最终温度。经煅烧的材料相似地在1200-1600℃下烧制足够的时间,烧制是在还原气氛如H2、CO、或这些气体之一与惰性气体的混合物、或通过椰子炭和含氧化合物的分解产物之间的反应所产生的气氛下进行,以使所有的经煅烧的材料转化成所希望的磷光体成分。
在本发明的另一个方面,当磷光体成分是非化学计算量时,磷光体具有更高量子效率。下面的表1表示磷光体通式为TbaAlbO12:Ce3+的磷光体获得了高量子效率,其中a/b两者都不是0.6并且b小于5。表1报告的相对量子效率是与标准铈活化铝酸钇石榴石磷光体进行对比的结果。
表1
样品批号 | a/b | b | 批规模(g) | 烧制条件 | 相对量子效率(%) |
D0213 | 0.594 | 4.9 | 150 | 包装在碳中 | 98 |
D0207 | 0.594 | 4.9 | 100 | 包装在碳中 | 93 |
D0208 | 0.594 | 4.9 | 100 | 在H2中烧制 | 97 |
D0215 | 0.594 | 4.9 | 250 | 包装在碳中 | 88 |
D0220 | 0.582 | 5 | 250 | 包装在碳中 | 88 |
D0225 | 0.613 | 4.75 | 250 | 在碳包装中烧制两次 | 92 |
发射白色光的装置
本发明的稀土活化含铽磷光体与包括在约400纳米到480纳米范围内发射蓝色光的发光二极管的装置结合,应该提供有效利用电能的白色光源。该白色光源可以通过使用一个蓝色光发光二极管制作成提供点光源装置或通过使用多个蓝色光发光二极管制作成大面积照明装置。
在如图3所示的本发明的一个具体实施例中,白色光源10包括在约400纳米到480纳米范围内发射蓝色光的发光二极管100和本发明的磷光体。发光二极管100安装在接近发光二极管100的具有反射性表面140的罩120中。适合于发射白色光装置的蓝色光发光二极管是基于InGaN半导体的发光二极管,例如上面提到的美国专利5,777,350中所披露的那些发光二极管,其结合于此作为参考。也可以使用其它紫外/蓝色光发光二极管,例如基于GaN半导体的发光二极管,其掺杂各种金属以提供较大的带隙。装备导电线150和152以对发光二极管100提供电能。透明铸件160包括环氧树脂、硅树脂、或玻璃180,其中分散有本发明的磷光体的基本均匀的颗粒200。可替换地,磷光体颗粒可以施加在发光二极管100上或只分散在透明铸件160的一部分之中。其它透明聚合物也可以用来形成透明铸件。另外,光散射材料的颗粒,例如TiO2或Al2O3,可以包括在透明铸件中并在磷光体颗粒之间,以改善从光源10发射出的光的均匀性。发光二极管的InGaN活性层的成分和在铸件中使用的磷光体的量可以进行选择,以便发光二极管发射的部分不被磷光体吸收的蓝色光与磷光体发射的宽光谱光结合,以提供具备所希望色温和显色指标(CRI)的白色光源10。
图4表示提供白色光的一定光源范围的色坐标,该光源可产生自蓝色光发光二极管和本发明的磷光体的各种组合。在图4中,点A表示本发明的磷光体(Tb0.97Ce0.03)3Al4.9O12的发射峰的坐标,点B和C则分别表示蓝色光发光二极管在450纳米和470纳米处的发射峰。线段AB和AC,其表示光源的色坐标,而这些光源结合有发光二极管和本发明的磷光体(Tb0.97Ce0.03)3Al4.9O12,表现出与普朗克或黑体曲线相交。此类相交点表示白色光源的色坐标,这些白色光源是适当的蓝色光发光二极管和磷光体(Tb0.97Ce0.03)3Al4.9O12的结合。对结合25%贡献的从蓝色光发光二极管发射的在470纳米的蓝色光,和75%贡献的从磷光体发射的光的装置,进行计算机模拟,得出色温为约4300K,发光度为每瓦特315流明,以及显色指标为76。使用15%贡献的从蓝色光发光二极管发射的在450纳米的蓝色光,和85%贡献的从同一磷光体发射的光进行相似的计算机模拟,得到的白色光源具有约3600K的色温,每瓦特342流明的发光度,以及65的显色指标。一种以上的本发明的磷光体可以加到同一装置中以提供颜色调整(color adjustment)。
用于一般照明的大面积白色光源可通过下述方法来制造:在平坦的反射板上安装多个蓝色光发光二极管,给单独的发光二极管提供适当的电导线,施加包括至少一种本发明的磷光体和聚合物粘结剂(如环氧树脂)的涂层,然后将整个结合结构密封在透明并密封的密封材料中。磷光体/聚合物涂层可以直接施加于单个的发光二极管或可以施加于整个板表面。在前面的情况下,在磷光体已施加于发光二极管上之后,可以在整个板表面上施加额外的聚合物涂层。另外,在聚合物基质中,可以提供惰性固体颗粒,如TiO2或Al2O3,以提高来自装置的光发射均匀性。
虽然本文叙述了多种具体实施例,从说明书中应该理解到,本领域技术人员可以进行各种要素结合、变化、等同替换、或改进,而不偏离本发明的范围,本发明的范围由所附权利要求所涵盖。
Claims (21)
1.一种稀土元素活化含铽石榴石磷光体,具有通式(Tb1-x-yAxREy)aDzO12;其中A是一种选自由Y、La、Gd、和Sm组成的组的成分;RE是一种选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、Lu、及其组合组成的组的成分;D是一种选自由Al、Ga、In、及其组合组成的组的成分;a的范围是从2.8到并且包括3;x的范围是从0到0.5;y的范围是从0.0005到0.2;4<z<5;并且对A进行选择以使A不同于RE。
2.根据权利要求1所述的稀土元素活化含铽石榴石磷光体,其中x的范围是从0到0.3;y的范围是从0.005到0.1;而z的范围是从4.6到小于5。
3.根据权利要求1所述的稀土元素活化含铽石榴石磷光体,具有通式(Tb1-yCey)3AlzO12,其中y的范围是从0.0005到0.2,而4<z<5。
4.根据权利要求3所述的稀土元素活化含铽石榴石磷光体,其中y的范围是从0.005到0.1,而z的范围是从4.6到小于5。
5.根据权利要求1所述的稀土元素活化含铽石榴石磷光体,其中所述磷光体具有通式(Tb1-yCey)3(Al1-r-sGarIns)zO12,其中y的范围是从0.0005到0.2,z的范围是从4.6到小于5,0<r≤0.5,0≤s≤0.5,并且r+s<1。
6.根据权利要求1所述的稀土元素活化含铽石榴石磷光体,其中所述磷光体具有通式(Tb1-yCey)3(Al1-r-sGarIns)zO12,其中y的范围是从0.0005到0.2,z的范围是从4到5,0≤r≤0.5,0<s≤0.5,并且r+s<1。
7.一种制造稀土元素活化含铽石榴石磷光体的方法,所述方法包括以下步骤:
提供一定量的铽的含氧化合物;至少一种稀土金属的含氧化合物,选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、和Lu组成的组;以及至少一种成分的含氧化合物,选自由Al、Ga、和In组成的组;
将所述含氧化合物共同混合以形成混合物;以及
在还原气氛下在一定温度烧制所述混合物足够的时间,使所述混合物转化成稀土元素活化含铽石榴石磷光体;
其中对所述量进行选择以使所述稀土元素活化含铽石榴石磷光体具有通式(Tb1-x-yAxREy)aDzO12;其中A是一种选自由Y、La、Gd、和Sm组成的组的成分;RE是一种选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、Lu、及其组合组成的组的成分;D是一种选自由Al、Ga、In、及其组合组成的组的成分;a的范围是从2.8到并且包括3;x的范围是从0到0.5;y的范围是从0.0005到0.2;4<z<5;并且对A进行选择以使A不同于RE。
8.一种制造稀土元素活化含铽石榴石磷光体的方法,所述方法包括下述步骤:
提供一定量的铽的含氧化合物;至少一种稀土金属的合氧化合物,所述稀土金属选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、和Lu组成的组;以及至少一种成分的含氧化合物,所述成分选自由Al、Ga、和In组成的组;
制备含有所述含氧化合物的第一种溶液;
提供含有碱的第二种溶液;
将所述第二种溶液加入到所述第一种溶液中以得到沉淀物;
分离所述沉淀物;
在氧化气氛下在一定温度将所述沉淀物煅烧足够的时间以使所述沉淀物脱水;以及
在还原气氛下在一定温度烧制所述混合物足够的时间,使所述混合物转化成稀土元素活化含铽石榴石磷光体。
9.根据权利要求7或8所述的方法,进一步包括在所述第一种溶液中加入至少一种金属的氟化物,所述金属选自由Tb、Al、Ga、In、Y、La、Ga、Sm、Ce、Pr、Nd、Eu、Dy、Ho、Er、Tm、Yb、和Lu组成的组。
10.根据权利要求7或8所述的方法,其中所述含氧化合物是选自由氧化物、硝酸盐、硫酸盐、醋酸盐、柠檬酸盐、氯酸盐、以及其组合组成的组。
11.根据权利要求8所述的方法,其中所述煅烧是在从400℃到1600℃的温度范围下进行。
12.根据权利要求8所述的方法,其中所述氧化气氛是选自由氧气、空气、以及其与一种惰性气体的混合物组成的组,所述惰性气体选自由氮气、氦气、氖气、氩气、氪气、和氙气组成的组。
13.根据权利要求7或8所述的方法,其中所述还原气氛包括气体选自由氢气、一氧化碳、其混合物、以及其与一种惰性气体的混合物组成的组,所述惰性气体选自由氮气、氦气、氖气、氩气、氪气、氙气、以及其混合物组成的组。
14.根据权利要求7或8所述的方法,其中所述烧制是在从900℃到1700℃的温度范围下进行。
15.一种发射白色光的光源,所述光源包括:
至少一个能够发射具有波长范围从近紫外到蓝色光的辐射的发光二极管;以及
涂层,所述涂层包括透明材料和稀土元素活化含铽石榴石磷光体的颗粒,所述磷光体包括铽和至少一种选自由铝、镓、和铟组成的组的元素;所述磷光体是用至少一种稀土金属离子所活化,所述稀土金属离子选自由铈、镨、钕、钐、铕、钆、镝、钬、铒、铥、镱、和镥组成的组;将所述涂层设置在接近所述至少一个发光二极管;所述磷光体吸收一部分从所述至少一个发光二极管发射的所述辐射并发射波长在可见区中的光;
其中所述稀土元素活化含铽石榴石磷光体具有通式(Tb1-x-yAxREy)aDzO12;其中A是选自由Y、La、Gd、和Sm组成的组的一种成分;RE是一种选自由Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Yb、Lu、及其组合组成的组的成分;D是一种选自由Al、Ga、In、及其组合组成的组的成分;a的范围是从2.8到并且包括3;x的范围是从0到0.5;y的范围是从0.0005到0.2;4<z<5;并且对A进行选择以使A不同于RE。
16.根据权利要求15所述的光源,其中由所述至少一个发光二极管发射的所述辐射是在从315纳米到480纳米的范围内,而所述磷光体能够发射具有从490纳米到770纳米的波长范围的光。
17.根据权利要求15所述的光源,所述稀土元素活化含铽石榴石磷光体,具有通式(Tb1-yCey)3(Al1-r-sGarIns)zO12,y的范围是从0.0005到0.2,而z的范围是从4到5,0≤r≤0.5,0<s≤0.5,并且r+s<1。
18.根据权利要求15所述的光源,其中x的范围是从0到0.3;y的范围是从0.005到0.1;而z的范围是从4.6到小于5。
19.根据权利要求15所述的光源,其中所述稀土元素活化含铽石榴石磷光体具有通式(Tb1-yCey)3AlzO12,其中y的范围是从0.0005到0.2,而z的范围是从4.6到小于5。
20.根据权利要求15所述的光源,其中所述稀土元素活化含铽石榴石磷光体具有通式(Tb1-yCey)3(Al1-r-sGarIns)zO12,其中y的范围是从0.0005到0.2,而z的范围是从4.6到小于5,0<r≤0.5,0≤s≤0.5,并且r+s<1。
21.根据权利要求15所述的光源,其中所述稀土元素活化含铽石榴石磷光体具有通式(Tb1-y-u-v-wCeyYuGdvSmw)3AlzO12,其中y的范围是从0.0005到0.2,z的范围是从4.6到小于5,0≤u、v、w≤0.5,并且0.0005≤y+u+v+w<1。
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-
2001
- 2001-06-01 US US09/681,522 patent/US6596195B2/en not_active Expired - Lifetime
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- 2002-05-29 WO PCT/US2002/017307 patent/WO2002099902A1/en active IP Right Grant
- 2002-05-29 AT AT02734622T patent/ATE385045T1/de not_active IP Right Cessation
- 2002-05-29 JP JP2003502902A patent/JP2004529252A/ja active Pending
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- 2002-05-29 DE DE60224798T patent/DE60224798T2/de not_active Expired - Fee Related
- 2002-05-29 KR KR10-2003-7015070A patent/KR20040012846A/ko not_active Application Discontinuation
- 2002-05-29 CN CNB028110412A patent/CN1269233C/zh not_active Expired - Fee Related
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EP1393385A1 (en) | 2004-03-03 |
ATE385045T1 (de) | 2008-02-15 |
WO2002099902A1 (en) | 2002-12-12 |
US20020195587A1 (en) | 2002-12-26 |
DE60224798D1 (de) | 2008-03-13 |
KR20040012846A (ko) | 2004-02-11 |
US6596195B2 (en) | 2003-07-22 |
EP1393385B1 (en) | 2008-01-23 |
TWI302937B (en) | 2008-11-11 |
CN1513209A (zh) | 2004-07-14 |
DE60224798T2 (de) | 2009-01-22 |
JP2004529252A (ja) | 2004-09-24 |
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