CN1654593A - 红色荧光粉及制法及发光二极管和活性动态液晶装置 - Google Patents

红色荧光粉及制法及发光二极管和活性动态液晶装置 Download PDF

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CN1654593A
CN1654593A CNA2004101033738A CN200410103373A CN1654593A CN 1654593 A CN1654593 A CN 1654593A CN A2004101033738 A CNA2004101033738 A CN A2004101033738A CN 200410103373 A CN200410103373 A CN 200410103373A CN 1654593 A CN1654593 A CN 1654593A
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姜允赞
赵济熙
孙哲守
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Korea Research Institute of Chemical Technology KRICT
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Abstract

本发明提供了一种式1所代表的红色荧光粉,其中M是选自K、Mg、Na、Ca、Sr和Ba中的元素,0≤x≤2,0.5≤y≤5,0.01≤z≤1.5和0.001≤q≤1.0。当红色荧光粉被特别是大约405nm的激发光源激发时,它具有例如高亮度的发射特性。该红色荧光粉的亮度是常规荧光粉的六倍。而且,红色荧光粉可以被用于有紫外激发光源的红色发光二极管(LED)、白色LED和活性动态液晶装置(LCD)。另外,使用红色荧光粉的白色LED具有90或更大的显色指数,并因此具有优良的彩色再现。(Li(2-z)-xMx)(MoO4)y∶Euz,Smq …(1)

Description

红色荧光粉及制法及发光二极管和活性动态液晶装置
技术领域
本发明涉及一种红色荧光粉(phosphor),尤其是涉及一种具有高的发射效率的红色荧光粉,一种制备该红色荧光粉的方法,以及一种红色发光二极管,一种白色发光二极管,和一种使用该红色荧光粉的活性动态液晶装置。
背景技术
白色发光二极管(LED)比白炽灯泡(通用的型号60W)有更长的寿命,可以制造成小的尺寸,并在低电压下工作。因此,白色LED被认为是在一些领域可供选择的光源,例如家用的荧光灯、液晶装置(LCD)的背光源等等。
白色LED可以用红色、绿色和蓝色LED来制造。在这种情况下,然而,白色LED需要高的制造成本,而且由于复杂的驱动线路而体积庞大。通过结合波长为450nm的InGaN基的蓝色LED和YAG:Ce荧光粉制造的白色LED已经被投入实际应用。该白色LED通过执行如下的步骤来运行。首先,蓝色LED发射蓝光。YAG:Ce荧光粉被一部分的蓝光激发,发射出黄绿色荧光。然后蓝光和黄绿色荧光合并形成白光。然而,这种白光仅具有可见光光谱的一部分,这导致小的显色指数(color rendering index)和差的色彩还原。另外,由于在这种情况下被用作光源的蓝色LED的波长为450nm,芯片效率低,因而白色LED的发射效率劣化。
为了解决上述问题,UV LED被用作激发光源,并且红色荧光粉、绿色荧光粉和蓝色荧光粉的组合被用于白色LED的制造工艺中以获得接近自然的白光。然而,最重要的是,当由约410nm的激发光源激发时,该波长处芯片效率最高,显示高发射效率的荧光粉是必要的前提。
目前,常规的蓝色荧光粉和绿色荧光粉具有好的发射效率。然而,因为红色荧光粉发射效率差,因此必须尽快开发被紫外激发光源激发时显示出高发射效率的红色荧光粉。
此外,被长波长的紫外光激发时显示出高发射效率的荧光粉的引入能促进活性动态LCD的改进。在活性动态LCD中,从背面的光源发射出来的光通过偏振器,然后通过液晶层。液晶层是否传送背光取决于它的方向。结果,背光按预定的方式被偏振化。偏振化后的光激发相应的荧光粉,其随后发光。因而,在前面的玻璃基板上形成图像。与常规的彩色LCD相比,活性动态LCD结构简单,并且容易制造。然而,由于常规红色荧光粉的发射亮度低,活性动态LCD在商业上是不适用的。特别的是,在活性动态LCD中,为了保护液晶,背面的光源必须是390nm或更大的长波长的紫外光。对于背面光源竞争性的选择物是UV LED。因此,被长波长的紫外光激发时显示出高效率的红色荧光粉的开发既有助于活性动态LCD的发展,又有助于红色LED和白色LED的改进。
目前,3.5MgO0.5MgF2GeO2:Mn,K5Eu(WO4)6.25被用作用于长波长紫外光的红色荧光粉。然而,3.5MgO0.5MgF2GeO2:Mn,K5Eu(WO4)6.25被400nm或更长的激发光源激发时显示出低的发射亮度和低的发射效率。
发明内容
本发明提供一种红色荧光粉,该红色荧光粉在被长波长的紫外激发光源激发时显示出高的发射效率。
本发明也提供一种制造红色荧光粉的方法。
本发明也提供一种包括红色荧光粉的红色发光二极管(LED)。
本发明也提供一种包括红色荧光粉的白色LED。
而且,本发明也提供一种包括红色荧光粉的活性动态液晶装置(LCD)。
根据本发明的一个方面,提供了一种式1所代表的红色荧光粉:
(Li(2-z)-xMx)(MoO4)y:Euz,Smq             ...(1)
其中M是选自K、Mg、Na、Ca、Sr和Ba中的一种元素,0≤x≤2,0.5≤y≤5,0.01≤z≤1.5和0.001≤q≤1.0。
根据本发明的另一方面,提供了一种制造红色荧光粉的方法,该方法包括在挥发性的极性溶剂中混合并分散一种化合物,该化合物选自Li、Eu、Mo和Sm的氧化物、碳酸盐、氯化物、氢氧化物、硫酸盐、氟化物、硝酸盐和醋酸盐,然后在600-1400℃下煅烧混合的浆液。
根据本发明的还一方面,提供了一种用式1所代表的红色荧光粉和380-420nm的UV LED组合所制造的红色LED。
根据本发明的又一方面,提供了一种通过组合式1所代表的红色荧光粉、绿色荧光粉和蓝色荧光粉的荧光粉组合及380-420nm的UV LED所制造的白色LED。
根据本发明的再一方面,提供了一种活性动态LCD,该活性动态LCD包括具有包含式1所代表的红色荧光粉的荧光粉图形的前面玻璃基板、液晶层和背面光源。
附图说明
通过参照附图来详细地描述典型的实施例,本发明的上述和其他的特征和优点将会更加明显,其中:
图1是说明本发明实施方案中的红色发光二极管(LED)的示意图;
图2是说明本发明实施方案中的活性动态液晶装置(LCD)的示意图;
图3是说明Eu的量固定而Sm的量变化时,红色荧光粉的相对亮度的变化;
图4是说明Sm的量固定而Eu的量变化时,红色荧光粉的相对亮度的变化;
图5是实施例7和11的吸收光谱;
图6是实施例7和预备实施例1的红色荧光粉的另一个吸收光谱;
图7是预备实施例1和实施例7中被394nm波长的激发光源激发时的红色荧光粉的发射光谱;
图8是预备实施例1和实施例7中被405nm波长的激发光源激发时的红色荧光粉的发射光谱;
图9是实施例12中的红色LED的发射光谱;和
图10是实施例13中的白色LED的发射光谱。
具体实施方式
依据本发明实施方案的红色荧光粉是用Li(MoO4)基的材料作为原材料制造的,以在被长波长的紫外(UV)光(380-420nm)激发时获得高的发射效率。这与常规的钾-钨和钠-钨基的红色荧光粉是相反的。特别的是,在红色荧光粉的制造方法中,Li(MoO4)被用作原材料,Eu被用作产生红色光的活性剂,并且添加Sm2O3作为回收剂。结果是,与现有的红色荧光粉相比,本发明的红色荧光粉在被例如400-410nm的长波长的紫外光激发时可具有高的发射特性。此外,Li(MoO4)中包含的锂可以被至少一种选自K、Mg、Na、Ca、Sr和Ba的元素替换以改变红色荧光粉的发射特性和物理性能。
依据本发明实施方案的红色荧光粉可以和适当量的常规红色荧光粉(3.5MgO0.5MgF2GeO2:Mn)(深红色荧光粉)混合来控制亮度和色彩纯度。
式1所代表的红色荧光粉可以通过固相方法、液相方法、或汽相方法来制造,但是并不限于此。制造红色荧光粉的固相方法包括在挥发性的极性溶剂中混合一种化合物,该化合物选自Li、Eu、Mo和Sm的氧化物、碳酸盐、氯化物、氢氧化物、硫酸盐、氟化物、硝酸盐和醋酸盐,然后在600-1400℃下煅烧混合溶液。例如,在挥发性的极性溶剂中混合并扩散碳酸锂(Li2CO3)、氧化铕(Eu2O3)、氧化钼(MoO3)和氧化钐(Sm2O3)。然后,混合溶液在例如氧化铝的反应器中在600-1400℃下进行煅烧。最后,洗涤化合物,产物是红色荧光粉。如果煅烧温度低于600℃,形成较少的晶体。如果煅烧温度大于1400℃,荧光粉分解,因而导致发射率的降低,以及使获得具有预定物理性能的粉末变得困难。由原材料而定,煅烧过程可以在大气压或降低的大气压中完成。
煅烧步骤可以在1-10个小时的时间内完成。如果煅烧时间小于1小时,形成较少的晶体。如果煅烧时间大于10小时,粉末变大,导致发射率降低,这也是不合乎需要的。
挥发性的极性溶剂可以是丙酮或乙醇,但不限于此。
本发明的红色发光二极管(LED)是通过将荧光粉注入到具有反射基体的杯状容器中制造的。参照图1,包括红色荧光粉(由式1所代表)的环氧模层6形成在LED芯片3上,芯片3在被380-420nm的长波长的紫外光激发时具有发射特性。通过阳极导线1和阴极导线2,阳极引线4和阴极引线5都分别地连接到LED芯片3上。包装材料7用无色或透有色光的树脂将环氧模层6及其周围模压并密封。
并且,本发明实施方案中的白色LED具有和红色LED同样的结构,除了所用的绿色荧光粉、蓝色荧光粉和红色荧光粉的RGB荧光粉组合之外。
绿色荧光粉可以是铝酸盐例如BaMgAl10O17:Mn2+,氯硅酸盐例如Ca8Mg(SiO4)Cl2:Eu2+,Mn2+等等,但是不限于此。优选的,绿色荧光粉可以是(Ba1-xSrx)SiO4:Eu2+(0≤x≤1)。
蓝色荧光粉可以是铝酸盐例如BaMg2Al16O27:Eu2+或BaMgAl10O17:Eu2+。优选地,蓝色荧光粉可以是(Srx(Mg,Ca)1-x)5PO4Cl:Eu2+(0≤x≤1)。
本发明实施方案中的白色LED具有为90或更大的显色指数,这大于用常规的蓝光LED和YAG:Ce荧光粉组合所制造的常规白色LED。因此,当本发明实施方案中的白色LED被用于照明时,可以获得近似自然光的具有优良的色彩还原(color rendition)的光。
图2是说明本发明的活性动态液晶装置(LCD)的示意图。图2说明活性动态LCD的通常结构。参照图2,380-420nm的光从背面的光源12释放,并通过偏振器14,然后通过液晶层16。液晶层16完成光的切换(switch)。然后,借助检偏器18,光照射到形成于前面玻璃基板20之上的预定荧光膜22上。荧光膜22被激发且发射出光。荧光膜22包括本发明制造的红色荧光粉。
参照下述的实施例将会进一步详细地描述本发明。下述的实施例被用于说明性的目的并不意味着限制本发明的范围。
预备实施例1
制造Li(2-z)(MoO4)2 :Euz 荧光粉
制备Li2CO3、Eu2O3和MoO3用作锂、Eu和Mo的前体。Li2CO3、Eu2O3和MoO3以适当的化学计量比与丙酮溶剂在研钵中混合。所得到的浆液置于氧化铝反应器中在空气存在下于600~1000℃煅烧3小时。用蒸馏水洗涤煅烧产物。活性材料Eu的量,其用z值表示,在0.01-1.3的范围内变化。当z为0.8时出现最佳的发射特性。当z大于0.8时,出现浓缩煅烧现象,降低发射。当Eu的浓度小于0.8时,活性剂的浓度太低,降低发射强度。当煅烧温度为900℃时呈现最佳的发射特性。当煅烧温度低于900℃时,形成较少的晶体而且颗粒较细,因而降低发射强度。当煅烧温度大于900℃时,颗粒变粗糙,并且发射面积减少,因而降低发射强度。
实施例1-5
制造Li(2-z)(MoO4)2 :Euz Smq 荧光粉
在这个过程中,按照与预备实施例1相同的方法制造红色荧光粉,除了Eu(z)的量固定为0.8且Sm(q)的量如表1所示变化以外。用394nm的激发光源测量红色荧光粉的相对发射强度。结果如图3所示。
[表1]红色荧光粉中Sm量的变化
    Sm(q)的量
    实施例1     0.02
    实施例2     0.04
    实施例3     0.06
    实施例4     0.08
    实施例5     0.10
如图3中表明的,Sm(q)的量为0.08的实施例4的相对发射强度最大。
实施例6-10
制造Li(2-z)(MoO4)2 :Euz Smq 荧光粉
按照与实施例1相同的方法制造红色荧光粉,除了Sm(q)的量固定为0.08而Eu(z)的量如表2所示变化以外。图4说明了红色荧光粉的相对发射强度。如图4中显而易见的,实施例7的相对发射强度最大。
[表2]红色荧光粉中Eu量的变化
    Eu(z)的量
    实施例6     0.7
    实施例7     0.8
    实施例8     0.9
    实施例9     1.0
    实施例10     1.1
实施例11
制造Na1.2Eu0.8(MoO4)2 :,Sm0.08 荧光粉
按照与预备实施例1相同的方法制造红色荧光粉,除了Eu(z)的量固定为0.8,Sm(q)的量固定为0.08并用Na代替Li以外。图5是实施例7和11所述的红色荧光粉的吸收波谱。每个吸收波谱在波长为362、382、394、417和465nm时具有尖峰。特别地是,在405nm实施例7的峰高大于实施例11的峰高,实施例11中包含Na而不是Li。
性能测试1
吸收波谱的观测
图6是预备实施例1和实施例7中所述红色荧光粉的吸收波谱。每个吸收波谱在波长为362、382、394、417和465nm时具有尖峰。特别地是,在405nm实施例7的峰高大于预备实施例1的峰高,实施例1中没有掺杂Sm。
性能测试2
吸收波谱的观测
预备实施例1和实施例7中制造的荧光粉被394nm的激发能源激发并发光。结果如图7所示。同样,荧光粉被405nm的激发能源激发并发光。结果如图8所示。参照图8,可以证实在波长405nm时实施例7的峰高是预备实施例1峰高的六倍,其中实施例7使用Sm而预备实施例1中没有用Sm。
实施例12
制造红色LED
用实施例7所述的红色荧光粉制造红色LED。该红色LED具有如图1所描述的常规的结构。图9是红色LED的发射波谱。根据图9,当使用400nm或更大的激发能源时,本发明的红色LED与常规的红色荧光粉相比具有高的发射效率。
实施例13
制造白色LED
首先,通过以重量比为2∶1∶15的比例混合作为蓝色荧光粉的(Srx(Mg,Ca)1-x)5PO4Cl:Eu2+,作为绿色荧光粉的(Ba1-xSrx)SiO4:Eu2+,实施例7所述的作为红色荧光粉的荧光粉来制备混合荧光粉。混合荧光粉和环氧树脂以1∶2的重量比例混合。用所得到的混合物涂覆UV LED来生产白色LED。图10说明了白色LED的发射波谱。如图10中显而易见的,与常规的白色LED相反,该白色LED的发射波谱在蓝色波长范围、绿色波长范围和红色波长范围内具有显著的波峰。结果表明根据本实施方案的白色LED具有优良的色彩再现能力。
当本发明的红色荧光粉被特别是大约405nm的激发光源激发时,它显示出高亮度的发射特性。红色荧光粉的亮度是常规荧光粉的六倍。因此,红色荧光粉可以被用于红色LED和有UV激发光源的白色LED以及活性动态LCD。另外,本发明的白色LED具有90或更大的显色指数,并因此具有优良的色彩再现。
尽管本发明参照其典型的实施方案已经得到了详细表述和描述,本领域的普通技术人员可以理解的是,在不偏离如下述权利要求所限定的本发明的精神和范围下,可以对其进行各种形式和细节上的变化。

Claims (9)

1.一种式1所代表的红色荧光粉:
        (Li(2-z)-xMx)(MoO4)y:Euz,Smq           ...(1)
其中M是选自K、Mg、Na、Ca、Sr和Ba的元素,0≤x≤2,0.5≤y≤5,0.01≤z≤1.5和0.001≤q≤1.0。
2.一种制造红色荧光粉的方法,所述方法包括:
在挥发性的极性溶剂中溶解选自Li、Eu、Mo和Sm的氧化物、碳酸盐、氯化物、氢氧化物、硫酸盐、氟化物、硝酸盐和醋酸盐中的化合物;
在600-1400℃下煅烧混合浆液;和
洗涤煅烧产物。
3.根据权利要求2所述的方法,其中挥发性的极性溶剂是丙酮或乙醇。
4.根据权利要求2所述的方法,其中煅烧进行1-10小时。
5.一种使权利要求1所述的红色荧光粉与380-420nm UV LED结合制造的红色发光二极管(LED)。
6.一种使权利要求1所述的红色荧光粉、绿色荧光粉和蓝色荧光粉的荧光粉组合与380-420nmUV LED结合制造的白色LED。
7.根据权利要求6所述的白色LED,其中绿色荧光粉是(Ba1-xSrx)SiO4:Eu2+(0≤x≤1)。
8.根据权利要求6所述的白色LED,其中蓝色荧光粉是(Srx(Mg,Ca)1-x)5PO4Cl:Eu2+(0≤x≤1)。
9.一种活性动态液晶装置(LCD),其包括:
具有荧光粉图形的前面玻璃基板,其包括权利要求1所述的红色荧光粉;
液晶层;和
背面的光源。
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Address before: Gyeonggi Do Korea Suwon

Patentee before: Samsung LED Co., Ltd.

Patentee before: Korea Research Institute of Chemical Technology