CN102844404A - 磷光体和含有它的leds - Google Patents
磷光体和含有它的leds Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims description 47
- 239000000843 powder Substances 0.000 abstract description 13
- 239000000919 ceramic Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000001429 visible spectrum Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 206010023126 Jaundice Diseases 0.000 description 4
- 208000004350 Strabismus Diseases 0.000 description 4
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000002223 garnet Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000001217 Terbium Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- -1 cerium activated yttrium aluminum garnet Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本文公开了用在LED应用中且特别是用在磷光体转换LEDs(pc-LEDs)中的磷光体。所述磷光体具有以(Y1-xCex)3(Al1-yScy)5O12表示的组成,其中0<x≤0.04且0<y≤0.6,并且其可作为透明烧结陶瓷应用到LED或者以粉末形式使用。通过调整该磷光体的组成,该磷光体可制成当被发蓝光的In-GaN LED激发时发出在可见光谱的绿光到黄色区域内的光。
Description
相关申请的交叉引用
本申请要求于2010年3月31日提交的美国临时申请No.61/319,666的权益。
技术领域
本发明涉及发光二极管(LED),更具体地涉及用在LED应用中的磷光体如磷光体转换LEDs。
背景技术
目前的白光发射磷光体转换LEDs(pc-LEDs)利用一种或多种磷光体来部分吸收来自InGaN LEDs的蓝光发射,以将部分蓝光转换为黄光。剩余未吸收的蓝光和转换的黄光组合产生感知为白色的光。在发黄光的磷光体之外,还可使用其它磷光体,例如发红光的磷光体,以提高显色指数(CRI)或得到不同的色温(CCT)。然而,发黄光的磷光体仍然是白光pc-LEDs中的核心组分。
pc-LED中通常采用的发黄光的磷光体是铈激活的钇铝石榴石,Y3Al5O12:Ce磷光体(YAG:Ce)。然而,其它磷光体包括记载在美国专利No.6,669,866中的铈激活的铽铝石榴石(TAG:Ce)磷光体,和硅酸盐基磷光体如记载在美国专利No.6,943,380、6,809,347、7,267,787和7,045,826中的那些。
YAG:Ce磷光体的实例及其在LED的应用记载在美国专利No.5,998,925中。该专利中还记载了YAG磷光体的一些组成变换,例如用Ga替换石榴石中的Al,或Gd替换Y。通常,Ga替代Al使发射峰向较短波长偏移,而Gd替代Y使发射峰向较长波长偏移。
发明概述
已经研制出用于发光二极管(LED)应用的新磷光体,其组成以(Y1-xCex)3(Al1-yScy)5O12表示,其中0<x≤0.04且0<y≤0.6。该磷光体发出的光的颜色可通过调整组成来改变。例如,一方面,该磷光体可在白光pc-LEDs中用作发黄光的磷光体。另一方面,该磷光体的组成可调节为使其可用作发绿光的磷光体,以将来自发蓝光的LED的蓝光发射全部转换为绿光发射。这是非常重要的,因为直接发绿光的InGaN LEDs具有非常低的效率。采用更高效率的发蓝光InGaN LEDs的发绿光的、完全转换pc-LED有可能提供更高效的绿光LEDs。
根据本发明的一方面,提供了具有以(Y1-xCex)3(Al1-yScy)5O12表示的组成的磷光体,其中0<x≤0.04且0<y≤0.6。
根据本发明的另一方面,提供了磷光体转换LED,其包括:发蓝光的LED和用于将该蓝光的至少一部分转换为波长不同的光的磷光体,该磷光体具有以(Y1-xCex)3(Al1-yScy)5O12表示的组成,其中0<x≤0.04且0<y≤0.6。
附图说明
图1图示了本发明磷光体转换LED(pc-LED)的实施方式。
图2图示了本发明pc-LED的可供选择的实施方式。
图3是根据本发明(实施例Y1)的具有组成(Y0.995Ce0.005)3(Al0.8Sc0.2)5O12的磷光体的发射光谱。
图4和图5是实施例Y1和Y3-Y9的磷光体的发射光谱。
图6是与常规(Y1-xCex)3(Al1-yGay)5O12磷光体相比,本发明不同磷光体组成的效率(lm/Wo-B)对Cx色坐标的坐标图。
发明详述
为了更好地理解本发明,以及它的其它和进一步的目的、优点和能力,下文公开内容和所附权利要求结合上述附图进行说明。
图1图示了本发明的磷光体转换LED 1的实施方式。在该实施方式中,磷光体转换器3是通过压制和烧结粉状磷光体或其氧化物前体形成的固体陶瓷件。磷光体转换器3放置在发蓝光的LED 5的顶部,该LED优选发射具有约420nm至约490nm的波长的光。此处显示LED 5安装在组件9中,该组件具有带反射壁(side)的凹陷(well)7,但本发明不限于这种特殊布置。
图2图示了本发明的可供选择的实施方式。在该实施方式中,磷光体转换LED 10封装在树脂15中,而磷光体颗粒13分分散在该树脂中。
实施例
利用商购的Y2O3、Al2O3、Sc2O3和CeO2氧化物粉末,制备不同组成的数种磷光体,这些氧化物粉末以一定量混合制成所需的组成(参见表1)。然后将混合的粉末压制成盘并在不同条件下烧结以形成磷光体。虽然这些样品成形为烧结陶瓷盘的形式,但是所述磷光体也可成形为粉末的形式。
批次(克) | Y2O3(克) | Al2O3(克) | Sc2O3(克) | CeO2(克) | 烧结气氛 |
Y1 | 2.7513 | 1.6447 | 0.5029 | 0.0211 | 湿H2 |
Y2 | 2.4623 | 0 | 2.5189 | 0.0189 | 湿H2 |
Y3 | 2.5988 | 0.786 | 1.5951 | 0.0199 | 湿H2 |
Y4 | 2.6592 | 1.4294 | 0.8286 | 0.0827 | 湿H2 |
Y5 | 2.7115 | 1.4356 | 0.8322 | 0.0208 | 湿H2 |
Y6 | 10.8864 | 5.7468 | 3.3306 | 0.0333 | 湿H2 |
Y7 | 11.2138 | 7.6108 | 1.1443 | 0.0347 | 湿H2 |
Y8 | 10.9668 | 6.203 | 2.7967 | 0.0343 | 湿H2 |
Y9 | 10.7322 | 4.8557 | 4.3781 | 0.0328 | 湿H2 |
实施例Y1
实施例Y1以额定组成(Y0.995Ce0.005)3(Al0.8Sc02)5O12进行制备。粉末混合物在300MPa压力下干法压制成盘。压制的盘在1800、1850、1880和1890℃在湿H2氛下烧结。所得烧结陶瓷为黄绿色。当烧结温度升高时,陶瓷变得更加半透明。当温度升高时,发光强度也增大。
蓝光激发下Y1发射的实例如图3所示。发射光谱显示出宽的黄光发射,峰值波长在533nm处。该发射光谱非常类似于YAG:Ce,表明该陶瓷具有石榴石结构。
实施例Y2
实施例Y2以额定组成(Y0.995Ce0.005)3Sc5O12进行制备。氧化物粉末混合并干法压制成盘。所述盘在1850℃和1900℃烧结。所得烧结陶瓷为橘红色。然而,在蓝光激发下没有观察到发射。
实施例Y3
实施例Y3以额定组成(Y0.995Ce0.005)3(Al0.4Sc0.6)5O12进行制备。通过干法压制氧化物粉末混合物然后在1850℃和1900℃烧结制备盘。当在1900℃烧结时,发生熔解,产生接近白色的主体颜色,而在1850℃烧结的盘具有黄绿色。Y3的发射具有527nm的峰值波长,与实施例Y1相比向较短波长偏移。
实施例Y4和Y5
实施例Y4和Y5分别以额定组成(Y0.98Ce0.02)3(Al0.7Sc0.3)5O12和(Y0.995Ce0.005)3(Al0.7Sc0.3)5O12进行制备。再次通过干法压制混合的氧化物粉末并在1850℃、1860℃和1800℃烧结制成盘。所得烧结陶瓷为半透明,其中Y4为黄色,而Y5为黄绿色。
实施例Y6
实施例Y6以额定组成(Y0.998Ce0.002)3(Al0.7Sc0.3)5O12进行制备。氧化物粉末与去离子水、聚合物粘合剂混合,并长时间球磨。然后干燥球磨后的浆料并研磨成粉末。通过在30k Psi下等静压(isopressing)制成盘。利用球磨使得氧化物更均匀混合并减少团聚。等静压的盘在湿H2氛下于1850℃、1860℃和1880℃烧结。得到几乎全透明的样品。
实施例Y7
实施例Y7以额定组成(Y0.998Ce0.002)3(Al0.9Sc0.1)5O12进行制备。氧化物粉末如实施例Y6进行球磨混合。压制的盘在1850℃和1880℃烧结。所得烧结盘为不透明的。
实施例Y8和Y9
实施例Y8和Y9分别制成具有额定组成(Y0.998Ce0.002)3(Al0.75Sc0.25)5O12和(Y0.998Ce0.002)3(Al0.6Sc0.4)5O12。氧化物粉末如实施例Y6进行球磨混合。等静压的盘在1860和1880℃烧结。发现两种组成都能烧结成几乎透明的。
除不显示发射的Y2之外,表2列出了上述实施例的蓝光激发发射的CIE1931色坐标(Cx,Cy)、主波长(Ldom)、峰值波长(Lpeak)、中心(centroid)波长(Lcentroid)和半宽度(FWHM)。Cx色坐标范围从约0.35至约0.44,且Cy色坐标范围从约0.55至约0.58。
对于第一组,实施例Y7、Y1、Y8、Y6、Y9和Y3,随着Sc浓度的百分比增加发射峰向可见光谱的绿色区域(较短波长)偏移。这种现象非常类似于提高(Y1-xCex)3(Al1-yGay)5O12中Ga替代Al的水平,表明在所述陶瓷中Sc可具有与Ga类似的结构作用。
表2
图4和5示出了实施例Y1和Y3-Y9的发射光谱。对于图5(实施例Y6、Y5和Y4),可看出随着Ce浓度增加(对于Y6、Y5和Y4分布为x=0.002、0.005和0.02)发射峰向可见光谱的黄色区域(较长波长)偏移。这也非常类似于YAG:Ce磷光体,在该磷光体中随着Ce浓度增加发射峰也向黄色偏移。
图6比较了本发明(Y1-xCex)3(Al1-yScy)5O12磷光体与常规(Y1-xCex)3(Al1-yGay)5O12磷光体的效率(Lm/Wo-B)与Cx色坐标的函数关系。效率量度,Lm/Wo-B,是白光pc-LED(发蓝光的LED管芯(die)加发黄光的磷光体)的流明值对不使用黄光磷光体的同一发蓝光LED管芯的光功率的比率。这使发蓝光的LED管芯的效能标准化并考虑了人眼对不同波长的视觉敏感度。因此这一量度更好地指示了磷光体的真实效能。然而,还应该说明的是,所述效率还涉及磷光体内的散射。然而,它仍可用于表明通常(Y1-xCex)3(Al1-yScy)5O12磷光体相比Y(AGa)G:Ce具有类似或更好的效率。对Y3、Y6、Y7和Y9测得的量子效率分别为90%、98%、92%和97%。
已经证明新磷光体能将InGaN LED发射的蓝光转换为绿光或黄光,并且能够用于白光pc-LEDs或完全转换绿光pc-LEDs。本发明的磷光体可以粉末或块状陶瓷形式使用。优选地,所述磷光体经过烧结形成为半透明的陶瓷件,其安装到发蓝光的LED管芯上以生成白光。对于完全转换型、绿光pc-LEDs,所述磷光体优选烧结成接近透明的陶瓷。所述磷光体也可用在远离发蓝光的LED的转换器元件。例如,包埋在安置为距LED或LEDs阵列一定距离的聚合物膜中,或者成形为安置在单个或多个LEDs上方的罩(dome)。
虽然,已经显示和描述了目前认为是本发明优选实施方式的具体实施方式,但是对本领域技术人员显而易见地,在不偏离所附权利要求限定的本发明范围的前提下可对此作出各种改变和变形。
Claims (6)
1.磷光体,其具有以(Y1-xCex)3(Al1-yScy)5O12表示的组成,其中0<x≤0.04且0<y≤0.6。
2.权利要求1的磷光体,其中激发时所述磷光体发出的光具有色坐标Cx和Cy,其中Cx在约0.35至约0.44的范围,且Cy在约0.55至约0.58的范围。
3.磷光体转换LED,其包括:发蓝光的LED和磷光体,该磷光体用于将所述蓝光的至少一部分转换为波长不同的光,所述磷光体具有以(Y1-xCex)3(Al1-yScy)5O12表示的组成,其中0<x≤0.04且0<y≤0.6。
4.权利要求3的磷光体转换LED,其中所述蓝光具有约420nm至约490nm的波长。
5.权利要求3的磷光体转换LED,其中被所述LED发出的蓝光激发时,所述磷光体发出的光具有色坐标Cx和Cy,其中Cx在约0.35至约0.44的范围,且Cy在约0.55至约0.58的范围。
6.权利要求5的磷光体转换LED,其中所述蓝光具有约420nm至约490nm的波长。
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