CN1769370B - 高cri电致发光灯 - Google Patents
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Abstract
一种具有高显色指数(CRI)的电致发光灯可以用一种荧光粉共混物制成，所述荧光粉共混物包含一种电致发光荧光粉和一种铕一活化的碱土硅氮化物荧光粉的混合物，其中所述电致发光荧光粉选自发蓝光的电致发光荧光粉、发蓝-绿光的电致发光荧光粉或它们的组合物。优选该灯的CRI至少约75，更优选至少约80。一种优选的共混物含有约10重量％-20重量％的铕-活化的碱土硅氮化物荧光粉。
Description
技术领域
本发明一般地涉及电致发光灯和荧光粉(phosphor)，以及，更具体地说，涉及产生白光的电致发光灯。
背景技术
电致发光(EL)是在电场激发下的光发射。基于该机理，EL灯因消费电子产品如蜂窝式电话和便携式计算设备日益增长的需求而在平板显示领域内获得越来越多的应用。EL灯也提供不依赖于视角的均匀光发射，而且它们对机械冲击和振动不敏感。它们很容易以1.5-9伏的直流电驱动，方法是使用在50-1000Hz的频率下产生约100-300V(峰对峰)的交流电压的转换器。
两种主要的EL灯构造一般叫作薄膜和厚膜。薄膜EL灯的制造方法是，用气相沉积法如CVD在玻璃基体上交替地沉积薄层介电材料、荧光粉和导电氧化物。厚膜灯的制造方法是，将粉末材料悬浮在树脂材料内，然后用传统的丝网印刷技术将悬浮料一层层涂布到塑料薄膜上。因此，厚膜EL灯可以是薄、柔性和牢固的，因而使它们适用于宽阔范围的照明应用。
厚膜EL灯可用的荧光粉主要由已掺杂多种活化剂如Cu、Au、Ag、Mn、Br、I和C1的硫化锌组成。这类荧光粉的实例已描述在U.S.专利5,009,808，5,702,643，6,090,311和5,643,496中。商品EL荧光粉的实例包括：OSRAM SYLVANIA型813，一种发蓝光的ZnS：Cu荧光粉；OSRAM SYLVANIA型723，一种发蓝-绿光的ZnS：Cu，Cl荧光粉和OSRAM SYLVANIA型523，一种发黄-橙光的ZnS：Cu，Mn荧光粉。一般而言，EL荧光粉的各颗粒都被无机涂层所包封，目的是提高它们的耐湿-引发降解性。这类涂层的实例描述在U.S.专利5,220,243，5,244,750，6,309,700和6,064,150中。
对于涉及多色信息显示的信号和背景照明，重要的是要能产生具有高显色指数(CRI)的白光。但是，最亮的电致发光荧光粉主要在约400nm-约550nm波长的蓝-绿光谱区发射。这就难以用EL灯获得高CRI的白光，尤其因为迄今尚未开发出令人满意的用于厚膜EL灯的发红光的电致发光荧光粉。目前，两种最主要的发白光的EL技术包括(1)使一种发蓝-绿光的电致发光荧光粉与一种绕丹宁染料组合以及(2)使一种发蓝-绿光的电致发光荧光粉和一种发橙光的ZnS：Cu，Mn电致发光荧光粉共混。在第一种情况下，蓝-绿电致发光荧光粉与绕丹宁染料的组合能产生CRI约为79以及x色坐标约为0.27和Y色坐标约为0.34的灯。但是，绕丹宁染料使未点亮的灯具有一种不理想的粉红色，这使它对于信号应用不够理想。在第二种情况下，共混的EL荧光粉产生的CRI只有约69以及x色坐标约为0.34和y色坐标约为0.38。此外，由于使用两种不同的EL荧光粉，会在灯的使用寿命期间因荧光粉的亮度衰减速率不同而存在色移问题。
中国专利出版物CN 1340590A描述了将发蓝光的和发蓝-绿光的EL荧光粉与一种铈-活化的钇铝石榴石荧光粉Y3Al5O12：Ce，(YAG：Ce)进行混合。YAG：Ce荧光粉是一种受蓝和蓝-绿EL荧光粉发射波长激发的光致发光荧光粉。YAG：Ce荧光粉发射的黄光与EL荧光粉发射的蓝或蓝-绿光产生白光。但是由这种组合发射的白光缺少明显的红组分，其结果，使CRI小于约70。
发明内容
本发明的一个目的是要避免现有技术中的缺点。
本发明的另一个目的是要提供一种具有高CRI的发白光的电致发光灯。
已经发现，高CRI电致发光灯可通过使一种发蓝光的或发蓝-绿光的EL荧光粉与一种铕-活化的碱土硅氮化物荧光粉组合而获得。优选发蓝光的电致发光荧光粉在约400nm-约470nm发射以及发蓝一绿光的电致发光荧光粉在约470nm-约550nm发射。铕-活化的碱土硅氮化物荧光粉是光致发光材料，它们在约200nm-约500nm波长下被激发并在黄-红光谱区内发射，且最大发射在约600nm-约680nm波长。
在一个实施方案中，铕-活化的碱土硅氮化物荧光粉可以用通式MxSiyNz：Eu表示，其中M选自Ca，Sr和Ba以及其中z＝2x/3+4y/3。这类碱土硅氮化物荧光粉已描述在U.S.专利6,682,663和6,649,946中，其在这里引入作为参考。在一个优选的实施方案中，碱土硅氮化物荧光粉由通式M2Si5N8：Eu表示，其中M选自Ca，Sr和Ba。一种更加优选的荧光粉是Ca2Si5N8：Eu。在另一个实施方案中，碱土荧光粉由通式MSi7N10：Eu表示，其中M选自Ca，Sr和Ba。优选Eu相对于碱土离子的浓度范围为1-10原子％。
当在电致发光灯中组合在一起时，来自电致发光和光致发光荧光粉的发射组合在一起产生具有高CRI的白光。优选灯的CRI至少约75。更优选CRI至少约80。优选的共混物含有电致发光荧光粉和约10重量％-20重量％的铕-活化的碱土硅氮化物荧光粉。其中电致发光荧光粉选自发蓝光的电致发光荧光粉、发蓝-绿光的电致发光荧光粉或它们的混合物。
附图说明
图1是按照本发明的厚膜电致发光灯的横截面示意图。
图2是两种电致发光荧光粉，即YAG：Ce荧光粉和铕-活化的碱土硅氮化物荧光粉的发射光谱的比较。
图3是CIE x，y色度图，示意从多种荧光粉组合可获得的色点。
具体实施方式
为更好地理解本发明及其另外的和更进一步的目的、优点及能力，要结合上述附图参考下述公开和所附权利要求。
参考图1，它示意按照本发明的一种厚膜电致发光灯2的横截面。灯2有两层介电层20和22.一种第一导电材料4，例如铝或石墨，涂在塑料膜12b上，形成灯2的第一电极，而一薄层透明导电材料6，如铟锡氧化物，涂在第二塑料薄膜12a上，形成第二电极。夹在两个导电电极4和6之间的是两层介电材料14的层20和层22，它们可以是，例如，氰乙基纤维素或氰乙基淀粉。与第一电极4毗邻的一层介电材料14中包埋有铁电材料10的颗粒，优选钛酸钡，与第二电极6毗邻的一层介电材料14中包埋有发蓝光的或发蓝一绿光的电致发光荧光粉8和铕-活化的碱土硅氮化物荧光粉7。
几种荧光粉的发射光谱在图2中进行比较：一种OSRAM SYLVANIA型813发蓝光的电致发光荧光粉、一种OSRAM SYLVANIA型723发蓝-绿光的电致发光荧光粉、一种铈-活化的钇铝石榴石(YAG：Ce)荧光粉和OSRAM型L350Ca2Si5N8：Eu荧光粉。Ca2Si5N8：Eu荧光粉的最大发射出现在约600nm，其大大高于YAG：Ce荧光粉约530nm的最大发射。
而且Ca2Si5N8：Eu荧光粉的发射扩展到约680nm。
制成含Ca2Si5N8：Eu荧光粉和发蓝光的发蓝-绿光的电致发光荧光粉的共混物的电致发光灯能产生高于约75的CRI值。而制成含相同的电致发光荧光粉和YAG：Ce的共混物的灯只能产生小于70的CRI值。
表1特地给出了从这类组合获得的CRI值的计算范围。
表1
| 荧光粉共混物 | CRI范围 |
| 813型(ZnS：Cu)&L350型Ca2Si5N8：Eu | 74-85 |
| 723型(ZnS：Cu，Cl)&L350型Ca2Si5N8：Eu | 75-85 |
| 813型(ZnS：Cu)&YAG：Ce | 56-68 |
| 723型(ZnS：Cu，Cl)&YAG：Ce | 53-62 |
图3示意发蓝光的(813)和发蓝-绿光的(723)电致发光荧光粉与YAG：Ce荧光粉(分别为曲线21和22)和Ca2Si5N8：Eu(L350)荧光粉(分别为曲线31和32)的共混物所能达到的CIEx，y色坐标范围。含L350荧光粉的共混物的曲线31，32与含YAG：Ce荧光粉的共混物的相应曲线21，22相比，前者更靠近黑体曲线且更接近于日光(0.333，0.333)、冷白(0.380，0.380)和温白(0.440，0.400)的白色点。(本文所说的x，y色坐标是按1931 Commission Internationale deI’Eclairage(CIE)Standard Observer(2°))。
用含约10重量％-约20重量％L350荧光粉的共混物可获得约85的CRI值。这种共混物的色坐标，对于x值，为约0.29-约0.39，对于y值，为约0.35-约0.39。表2比较了用含20重量％的电致发光荧光粉，即YAG：Ce(OSRAM SYLVANIA 251型)和Ca2Si5N8：Eu(L350)的共混物制造的几种EL灯的数据。
表2
| 荧光粉 | 亮度(ft-L) | 效率(流明/瓦) | X | y | CRI |
| 813(对比) | 20.3 | 2.92 | 0.170 | 0.250 | 30 |
| 813/251 | 17.8 | 3.19 | 0.217 | 0.345 | 55 |
| 813/L350 | 16.7 | 3.44 | 0.295 | 0.356 | 85 |
| 723(对比) | 31.9 | 4.18 | 0.188 | 0.423 | 40 |
| 723/L350 | 18.8 | 4.29 | 0.314 | 0.490 | 75 |
虽然已示出并描述了目前认为是本发明的优选实施方案，但对本领域内的技术人员来说，显然在其中可以做各种变更和修改而不偏离所附权利要求所定义的本发明的范围。
Claims (27)
1.一种电致发光灯，包括一种由电致发光荧光粉和铕-活化的碱土硅氮化物荧光粉的混合物组成的荧光粉共混物，该电致发光荧光粉选自发蓝光的电致发光荧光粉、发蓝-绿光的电致发光荧光粉或它们的组合。
2.权利要求1的灯，其中铕-活化的碱土硅氮化物荧光粉由通式MXSiyNZ:Eu表示，其中M选自Ca，Sr和Ba，以及其中z＝2x/3+4y/3。
3.权利要求1的灯，其中铕-活化的碱土硅氮化物荧光粉由通式M2Si5N8:Eu表示，其中M选自Ca，Sr和Ba。
4.权利要求1的灯，其中铕-活化的碱土硅氮化物荧光粉由通式MSi7N10:Eu表示，其中M选自Ca，Sr和Ba。
5.权利要求1的灯，其中铕-活化的碱土硅氮化物荧光粉是Ca2Si5N8:Eu。
6.权利要求1的灯，其中所述共混物含有10重量％-20重量％的铕-活化的碱土硅氮化物荧光粉。
7.权利要求1的灯，其中发蓝光的电致发光荧光粉是ZnS:Cu以及发蓝-绿光的电致发光荧光粉是ZnS:Cu，Cl。
8.权利要求1的灯，其中发蓝光的电致发光荧光粉在400nm-470nm波长发射以及发蓝-绿光的电致发光荧光粉在470nm-550nm波长发射。
9.权利要求8的灯，其中铕-活化的碱土硅氮化物荧光粉在200nm-500nm波长被激发以及在600nm-680nm波长呈现最大发射。
10.权利要求1的灯，其中该灯的CRI至少为75。
11.权利要求1的灯，其中该灯的CRI至少为80。
12.权利要求5的灯，其中该灯的CRI为85。
13.权利要求1的灯，其中该灯的x色坐标为0.29-0.39以及y色坐标为0.35-0.39。
14.权利要求13的灯，其中所述共混物含有10重量％-20重量％的铕-活化的碱土硅氮化物荧光粉。
15.权利要求14的灯，其中铕-活化的碱土硅氮化物荧光粉是Ca2Si5N8:Eu。
16.权利要求2的灯，其中铕相对于碱土离子的浓度为1-10原子％。
17.一种荧光粉共混物，它包含：电致发光荧光粉和铕-活化的碱土硅氮化物荧光粉的混合物，所述电致发光荧光粉选自发蓝光的电致发光荧光粉、发蓝-绿光的电致发光荧光粉或它们的组合，其中该共混物含有10重量％-20重量％的铕-活化的碱土硅氮化物荧光粉。
18.权利要求17的荧光粉共混物，其中铕-活化的碱土硅氮化物荧光粉由通式MxSiyNz:Eu表示，其中M选自Ca，Sr和Ba，以及其中z＝2x/3+4y/3。
19.权利要求17的荧光粉共混物，其中铕-活化的碱土硅氮化物荧光粉由通式M2Si5N8:Eu表示，其中M选自Ca，Sr和Ba。
20.权利要求17的荧光粉共混物，其中铕-活化的碱土硅氮化物荧光粉由通式MSi7N10:Eu表示，其中M选自Ca，Sr和Ba。
21.权利要求17的荧光粉，其中铕-活化的碱土硅氮化物荧光粉是Ca2Si5N8:Eu。
22.权利要求18的荧光粉共混物，其中发蓝光的电致发光荧光粉是ZnS:Cu和发蓝-绿光的电致发光荧光粉是ZnS:Cu，Cl。
23.权利要求17的荧光粉共混物，其中发蓝光的电致发光荧光粉在400nm-470nm波长发射和发蓝-绿光的电致发光荧光粉在470nm-550nm波长发射，以及铕-活化的碱土硅氮化物荧光粉在200nm-500nm波长被激发并在600nm-680nm波长呈现最大发射。
24.权利要求18的荧光粉共混物，其中铕相对于碱土离子的浓度为1-10原子％。
25.一种荧光粉共混物，它包含电致发光荧光粉和Ca2Si5N8:Eu荧光粉的混合物，所述电致发光荧光粉选自发蓝光的ZnS:Cu荧光粉、发蓝-绿光的ZnS:Cu，Cl荧光粉或它们的组合。
26.权利要求25的荧光粉共混物，其中铕相对于碱土离子的浓度是1-10原子％。
27.权利要求25的荧光粉共混物，其中该共混物含有10重量％-20重量％的Ca2Si5N8:Eu荧光粉。
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| JP2012227157A (ja) | 2012-11-15 |
| US20060066209A1 (en) | 2006-03-30 |
| JP2006108090A (ja) | 2006-04-20 |
| EP1642952B1 (en) | 2013-10-09 |
| KR20060051687A (ko) | 2006-05-19 |
| KR101263497B1 (ko) | 2013-05-13 |
| US8278816B2 (en) | 2012-10-02 |
| CA2511250A1 (en) | 2006-03-30 |
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Owner name: GLOBAL TUNGSTEN + POWDERS CORP. Free format text: FORMER OWNER: OSRAM SYLVANIA INC. Effective date: 20140825 |
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