CN106281320A - 荧光粉、其制备方法及包含其发光装置与背光模块 - Google Patents
荧光粉、其制备方法及包含其发光装置与背光模块 Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 122
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- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 abstract description 7
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 abstract description 6
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
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- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
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Abstract
本发明提供一种荧光粉，具有下列化学式：K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，其中荧光粉具有六方晶相的P63mc空间群。本发明也提供上述荧光粉的制备方法及包含其发光装置与背光模块。本发明的荧光粉可应用于蓝光发光二极管使其产生红光荧光，也可于蓝光发光二极管中搭配YAG黄光荧光粉(Y3Al5O12:Ce；钇铝石榴石)及/或绿光荧光粉使其产生白光，以增加演色性。
Description
技术领域
本发明涉及一种荧光粉、其制备方法及包含其发光装置与背光模块，特别涉及一种可提高演色性的荧光粉、其制备方法及包含其的发光装置与背光模块。
背景技术
近年来，各国节约能源与环境保护概念成长，作为新世代照明来源，发光二极管(Light-emitting Diodes；LEDs)可解决传统白炽灯与日光灯所面临难以克服的问题，同时兼具省电与环保概念，故促使新能源的开发与提高能源效率的议题受大众重视。其中，彩色发光二极管已普遍用于色彩照明、显示器、娱乐产品等，其中以电子显示器产业为发展最迅速的领域，相信未来在光电组件上的应用将会扮演重要角色。
目前全球LED的发展以RGB高演色性白光发光二极管(WhiteLight-emitting Diodes；WLEDs)为主要发展方向，白光发光二极管具有体积小、热辐射小、寿命长且耗电量低等优点，更显现白光发光二极管在新世代照明领域中的发展价值。
以YAG荧光粉(Y3Al5O12:Ce；钇铝石榴石)搭配蓝光LED芯片是目前业界最常用以制造白光LED的方式之一，然而，为弥补YAG荧光粉(Y3Al5O12:Ce；钇铝石榴石)所欠缺的红色光谱，添加发红光的荧光粉的白光LED工艺已成为新课题，目前已有许多红光荧光粉的合成与应用信息，例如：已知A2[MF6]:Mn4+(其中A为Li,Na,K,Rb,Cs,NH4，M为Ge、Si、Sn、Ti与Zr)氟化物可作为LED的红光荧光粉材料。
由上可知，可用于提高白色LED演色性的红光荧光粉及其制备方法，为当前LED发展的重要目标之一。
发明内容
根据一实施例，本发明提供一种荧光粉，具有下列化学式：K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，其中荧光粉具有六方晶相的P63mc空间群。
根据另一实施例，本发明提供一种荧光粉的制备方法，包括：(a)提供一初始荧光粉，其化学式为：K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，其中初始荧光粉具有六方晶相的空间群；(b)实施一热处理，使得初始荧光粉相变为具有六方晶相的P63mc空间群的一荧光粉。
根据另一实施例，本发明提供一种发光装置，包括：一激发光源；一发光材料，配置于激发光源上，其中发光材料包括：一荧光粉，具有下列化学式：K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，其中荧光粉具有六方晶相的P63mc空间群。
又根据另一实施例，本发明提供一种背光模块，包括至少一如前述的发光装置。
本发明的荧光粉可应用于蓝光发光二极管使其产生红光荧光，也可于蓝光发光二极管中搭配YAG黄光荧光粉(Y3Al5O12:Ce；钇铝石榴石)及/或绿光荧光粉使其产生白光，以增加演色性。
为让本发明的上述和其他目的、特征与优点能更明显易懂，下文特举出较佳实施例，并配合所附附图，作详细说明如下：
附图说明
图1A、图1B为根据本发明一些实施例显示发光装置的剖面示意图；
图2A为根据本发明一实施例所制备的K2Ge0.95F6:Mn0.05 4+荧光粉于不同加热温度下的放射光谱图谱；
图2B为根据本发明一实施例所制备的K2Ge0.95F6:Mn0.05 4+荧光粉于冷却温度(300～25℃)下的放射光谱图谱；
图3为根据本发明一实施例所制备的K2Ge0.95F6:Mn0.05 4+荧光粉于不同加热温度下的X光粉末绕射图谱；
图4为根据本发明一实施例所制备的K2Ge0.95F6:Mn0.05 4+荧光粉于不同加热温度下的晶体结构示意图；
图5为根据本发明一实施例所制备的K2Ge0.95F6:Mn0.05 4+荧光粉于加热前后的拉曼光谱图；
图6为根据本发明一实施例所制备的K2Ge0.95F6:Mn0.05 4+荧光粉于加热前后与蓝光LED芯片(发光波长介于400～500nm)搭配YAG黄光荧光粉产生的白光光谱图。
其中，附图标记说明如下：
100～发光装置
102～激发光源
104～发光材料
106～导线架
108～透明树脂
110～封装材
200～发光装置
202～激发光源
204～发光材料
206～透射光学组件
具体实施方式
本发明提供一种能够提高演色性的荧光粉及其制备方法。以热处理的方式使K2[Ge1-xF6]:Mnx 4+荧光粉的结构从六方晶相空间群相变成六方晶相的P63mc空间群，进而产生零声子线(zero phonon line；ZPL)，所形成的荧光粉可应用于蓝光发光二极管使其产生红光荧光，或可应用于白光发光二极管以增加其演色性。
在一实施例中，本发明提供一种荧光粉，其具有下列化学式：K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，此荧光粉具有六方晶相的P63mc空间群。在本发明一实施例中，荧光粉的化学式可为K2Ge0.95F6:Mn0.05 4+。此荧光粉经由波长介于320～500nm的光激发后，可放射出波长介于600～650nm的红光，并且在波段620～625nm具有一零声子线(zero phonon line；ZPL)。
值得注意的是，上述可激发本发明提供的红光荧光粉的光波长范围避开黄光的波段(约570～590nm)，因此以含有发光二极管的发光装置为例，黄光荧光粉被发光二极管(例如:蓝光发光二极管)所激发出的黄光被本发明的红光荧光粉吸收的机率很低，故可避免黄光损失并同时由本发明的荧光粉提供红光，进而提升发光装置的演色性。此外，应可注意到的是，上述可激发本发明提供的红光荧光粉的光波长范围也避开了绿光的波段(约495～570nm)，因此绿光荧光粉被发光二极管(例如:蓝光发光二极管)所激发出的绿光被本发明的红光荧光粉吸收的机率很低，故也可避免绿光损失并同时由本发明的荧光粉提供红光，进而达到提升发光装置演色性的目的。因此，在波长介于320～500nm的范围中，只要满足上述条件，均可作为本发明提供的荧光粉的激发光。
在另一实施例中，本发明也提供上述荧光粉的制备方法。首先，提供一初始荧光粉，其化学式为：K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，此初始荧光粉具有六方晶相的空间群。在本发明一实施例中，此初始荧光粉的化学式可为K2Ge0.95F6:Mn0.05 4+。接着，对初始荧光粉实施一热处理，此热处理可在250℃～450℃下，例如：300℃～400℃、400℃～425℃、或425℃～450℃，持续约10～30分钟，例如：20分钟，使得上述具有六方晶相空间群的K2[Ge1-xF6]:Mnx 4+初始荧光粉相变成具有六方晶相的P63mc空间群的K2[Ge1-xF6]:Mnx 4+荧光粉，进而产生零声子线(zero phonon line；ZPL)于波段620～625nm。
上述的初始荧光粉K2[Ge1-xF6]:Mnx 4+可经由例如：两阶段化学共沉淀法(two-step chemical co-precipitation)、或其他合适的工艺形成。
在另一实施例中，本发明提供一种发光装置，包括：一激发光源，以及一发光材料，配置于激发光源上。上述激发光源可包括一发光二极管(Light-emitting Diode；LED)，其发光波长介于320～500nm，例如：蓝光发光二极管，其发光波长介于400～500nm，较佳介于440～480nm。
于一实施例中，发光材料可包括：一荧光粉，其具有下列化学式：K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，此荧光粉具有六方晶相的P63mc空间群。此荧光粉经由波长介于320～500nm的光激发后，可放射出波长介于600～650nm的红光，且于波段620～625nm具有一零声子线(zero phonon line；ZPL)。
于一实施例中，本发明的K2[Ge1-xF6]:Mnx 4+荧光粉可与其他荧光粉混合。例如，发光材料可还包括一放射黄光的荧光粉(例如：YAG黄光荧光粉、硅酸盐类黄光荧光粉)，及/或一放射绿光的荧光粉(例如：β-SiAlON绿光荧光粉)。此放射黄光的荧光粉及/或放射绿光的荧光粉可与本发明提供的红光荧光粉混合，经由蓝光激发后放射出白光。于上述混合荧光粉中，放射黄光、绿光、及红光的荧光粉的比例并无限制，任两者之间的比例可介于1：99～99：1的范围内，例如可为1：1：1，可依实际需求及荧光粉的性质加以调整。上述作为激发光的蓝光波长可介于400～500nm，较佳介于440～480nm。值得注意的是，上述可激发本发明提供的红光荧光粉的光波长范围避开了黄光的波段(约570～590nm)和绿光的波段(约495～570nm)，因此在具有可放射黄光及/或绿光的荧光材料的发光装置像是发光二极管(如蓝光发光二极管)中，可避免黄光及/或绿光的损失，并同时由本发明提供的荧光粉提供红光，进而达到提升发光装置演色性的目的。
图1A为根据本发明一实施例显示一发光装置100的剖面示意图。发光装置100包括：一激发光源102，以及一发光材料104，配置于激发光源102上。在此实施例中，激发光源102为一蓝光发光二极管，其配置于一导线架106上。混合有发光材料104的透明树脂108包覆着激发光源102。封装材110用以封装激发光源102、导线架106、和透明树脂108。应理解的是，上述发光装置的配置方式及示意图仅为本发明众多实施例之一，本发明并不限于此，本领域普通技术人员可依据本发明的教示并参酌现有技术加以修改或润饰。
图1B为根据本发明另一实施例显示一发光装置200的剖面示意图。发光装置200包括：一激发光源202，以及一发光材料204，配置于激发光源202上。在此实施例中，一透射光学组件206配置于发光材料204上，其具有光取出性质。透射光学组件206可为一或多层聚合物层、硅层、或树脂层。
又在一实施例中，本发明提供一种背光模块，其包括至少一前述的发光装置，有关发光装置的详细内容与前述类似，故不再此赘述。背光模块可应用于显示器(例如液晶显示器)，作为显示器的直下式背光模块或侧光式背光模块。
例如，背光模块包括发白光的发光装置。发光装置包括一发蓝光或UV光或近UV光的激发光源、发绿光的荧光粉与本发明的发红光的K2[Ge1-xF6]:Mnx 4+荧光粉，其中激发光源的发光波长为320～500nm。
以下提供各实施例说明本发明荧光粉的制备方法、结构、其特性：
实施例1：荧光粉K2Ge0.95F6:Mn0.05 4+的制备
将0.2000g的六氟锰二钾(K2MnF6)溶于1.3911g/7.5mL的二氧化锗/氢氟酸(GeO2/HF)溶液中，接着逐滴加入KF/HF溶液(2.3250g/7.5mL)，产生黄色沉淀物，之后过滤反应生成的沉淀物，分三次加入20mL的乙醇，并放置于50℃的烘箱中进行干燥，即可得到荧光粉K2Ge0.95F6:Mn0.05 4+。
实施例2：量测荧光粉K2Ge0.95F6:Mn0.05 4+的放射光谱图谱
对实施例1所制备的荧光粉K2Ge0.95F6:Mn0.05 4+进行热处理，并量测荧光粉K2Ge0.95F6:Mn0.05 4+于不同加热温度下的放射光谱图谱以及荧光粉K2Ge0.95F6:Mn0.05 4+于冷却温度(300～25℃)下的放射光谱图谱，其结果分别显示于图2A、图2B。于图2B中，可清楚地观察到零声子线(ZPL)产生，其光谱位置位于620～625nm。
实施例3：量测荧光粉K2Ge0.95F6:Mn0.05 4+的X光粉末绕射图谱
利用X光粉末绕射仪鉴定本发明实施例1所制备的荧光粉K2Ge0.95F6:Mn0.05 4+于不同加热温度下的X光粉末绕射图谱，其结果显示于图3，可清楚地观察到荧光粉K2Ge0.95F6:Mn0.05 4+的结构相变效应。其中，图3下方三列所示的无机晶格数据库(inorganic crystal structure database,ICSD)为JCPDS(Joint Committee on Powder Diffraction Standards)的标准图谱，其分别显示出三种晶系空间群的标准图谱，第1相为空间群、第2相为P63mc空间群、第3相为Fm3m空间群。
将实施例1所制备的荧光粉K2Ge0.95F6:Mn0.05 4+于不同加热温度下的X光粉末绕射图谱与标准图谱进行对照后，可观察到，于加热温度20℃、200℃时，荧光粉K2Ge0.95F6:Mn0.05 4+为纯相，具有对应于第1相的空间群晶体结构。在加热温度为250℃时，荧光粉K2Ge0.95F6:Mn0.05 4+同时具有对应于第1、2相的和P63mc空间群晶体结构，但以第1相为主，于图3中以(2+1)表示。在加热温度为300℃时，荧光粉K2Ge0.95F6:Mn0.05 4+也同时具有对应于第1、2相的和P63mc空间群晶体结构，但此时以第2相为主，于图3中以(2+1)表示。在加热温度为400℃时，荧光粉K2Ge0.95F6:Mn0.05 4+为纯相，具有对应于第2相的P63mc空间群晶体结构。在加热温度为425℃、450℃时，荧光粉K2Ge0.95F6:Mn0.05 4+同时具有对应于第2、3相的P63mc和Fm3m空间群晶体结构，但分别以第2相、第3相为主，于图3中以(2+3)、(3+2)表示。而在加热温度为500℃时，荧光粉K2Ge0.95F6:Mn0.05 4+为纯相，具有对应于第3相的Fm3m空间群晶体结构。
上述结果证实，本发明成功通过热处理使得荧光粉K2Ge0.95F6:Mn0.05 4+的晶体结构产生相变，特别是在热处理的温度介于250℃～450℃时，原本空间群为的荧光粉K2Ge0.95F6:Mn0.05 4+会相变为空间群为P63mc的荧光粉K2Ge0.95F6:Mn0.05 4+。
综合实施例2～3及图2～3所示结果可知，当热处理的温度介于250℃～450℃时，荧光粉K2Ge0.95F6:Mn0.05 4+会产生对应于第2相的P63mc空间群晶体结构，于此晶体结构下，荧光粉K2Ge0.95F6:Mn0.05 4+可放射出红光荧光并具有零声子线。而最初实施例1所制备的未经热处理的荧光粉K2Ge0.95F6:Mn0.05 4+，其晶体结构的空间群为其虽然也可放射出红光荧光，但并不具有零声子线。
实施例4：荧光粉K2Ge0.95F6:Mn0.05 4+于不同加热温度下的晶体结构示意图
图4显示实施例1所制备的荧光粉K2Ge0.95F6:Mn0.05 4+于不同加热温度下的晶体结构示意图，其结构对应于图3所观察到的结果。由图4可看到，未经过热处理的荧光粉K2Ge0.95F6:Mn0.05 4+原本为六方晶相的空间群，随着热处理的温度增加，其晶体结构逐渐出现六方晶相的P63mc空间群，直到温度为400℃时，荧光粉K2Ge0.95F6:Mn0.05 4+完全相变为具有六方晶相的P63mc空间群的纯相。随着热处理的温度继续增加，其晶体结构逐渐出现Fm3m空间群，直到温度为500℃时，荧光粉K2Ge0.95F6:Mn0.05 4+完全相变为具有Fm3m空间群的纯相。
实施例5：荧光粉K2Ge0.95F6:Mn0.05 4+于热处理前后的拉曼光谱图
图5显示实施例1所制备的荧光粉K2Ge0.95F6:Mn0.05 4+于热处理(400℃煅烧0.5h)前后的拉曼光谱图。上方的图谱为实施例1所制备的荧光粉经热处理后的拉曼光谱图，下方的图谱为实施例1所制备的荧光粉经热处理前的拉曼光谱图。从图5可清楚地观察到荧光粉K2Ge0.95F6:Mn0.05 4+于热处理前后其振动模式ν1(A1g)、ν2(Eg)、ν3(T1u)、ν4(T1u)、ν5(T2g)、和ν6(T2u)信号强弱所有变化，代表荧光粉K2Ge0.95F6:Mn0.05 4+于热处理前后其晶体结构的确产生改变。
实施例6：荧光粉K2Ge0.95F6:Mn0.05 4+于热处理前后于蓝光LED芯片中搭配YAG黄光荧光粉产生的白光光谱图
图6显示实施例1所制备的荧光粉K2Ge0.95F6:Mn0.05 4+于热处理(400℃煅烧0.5h)前后与蓝光LED芯片搭配YAG黄光荧光粉(Y3Al5O12:Ce；钇铝石榴石)产生的白光光谱图。上图显示实施例1所制备的荧光粉经热处理后的白光光谱图，下图显示实施例1所制备的荧光粉经热处理前的白光光谱图谱。从图6可清楚地观察到经热处理后的荧光粉有零声子线(ZPL)产生，其光谱位置位于620～625nm。
综上所述，本发明提供一种荧光粉的制备方法，其通过热处理(250～450℃)的方式使K2[Ge1-xF6]:Mnx 4+荧光粉的结构从六方晶相空间群相变成六方晶相的P63mc空间群，进而产生零声子线(zero phonon line；ZPL)，所形成的荧光粉可应用于蓝光发光二极管使其产生红光荧光，也可于蓝光发光二极管中搭配YAG黄光荧光粉(Y3Al5O12:Ce；钇铝石榴石)及/或绿光荧光粉使其产生白光，以增加演色性。
虽然本发明已以数个较佳实施例公开如上，然其并非用以限定本发明，任何本领域普通技术人员，在不脱离本发明的精神和范围内，当可作任意的更动与润饰，因此本发明的保护范围当视后附的权利要求所界定者为准。
Claims (15)
1.一种荧光粉，具有下列化学式：
K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，
其中该荧光粉具有六方晶相的P63mc空间群。
2.如权利要求1所述的荧光粉，其中该荧光粉于波段620～625nm具有一零声子线。
3.如权利要求1所述的荧光粉，其中该荧光粉经由波长介于320～500nm的光激发后，放射出波长介于600～650nm的红光。
4.一种荧光粉的制备方法，包括：
(a)提供一初始荧光粉，其化学式为：
K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，其中该初始荧光粉具有六方晶相的P3m1空间群；
(b)实施一热处理，使得该初始荧光粉相变为具有六方晶相的P63mc空间群的一荧光粉。
5.如权利要求4所述的制备方法，该热处理是在250℃～450℃下持续约20分钟。
6.如权利要求4所述的制备方法，该热处理是在400℃下持续约20分钟。
7.如权利要求4所述的制备方法，其中该荧光粉于波段620～625nm具有一零声子线。
8.如权利要求4所述的制备方法，其中该荧光粉经由波长介于320～500nm的光激发后，放射出波长介于600～650nm的红光。
9.一种发光装置，包括：
一激发光源；以及
一发光材料，配置于该激发光源上，其中该发光材料包括：
一荧光粉，具有下列化学式：
K2[Ge1-xF6]:Mnx 4+，其中0<x<0.2，
其中该荧光粉具有六方晶相P63mc的点群结构。
10.如权利要求9所述的发光装置，其中该激发光源包括一发光二极管，其发光波长介于320～500nm。
11.如权利要求9所述的发光装置，其中该荧光粉于波段620～625nm具有一零声子线。
12.如权利要求9所述的发光装置，其中该荧光粉经由该激发光源所发出的光激发后，放射出波长介于600～650nm的红光。
13.如权利要求9所述的发光装置，其中该发光材料还包括一放射黄光的荧光粉及/或一放射绿光的荧光粉。
14.如权利要求13所述的发光装置，其中该发光装置产生白光。
15.一种背光模块，包括至少一如权利要求9～14中任一项所述的发光装置。
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| US10040994B2 (en) | 2018-08-07 |
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