CN114478008B - 一种固态照明用高显色指数高热稳定性的荧光陶瓷及其制备方法 - Google Patents
一种固态照明用高显色指数高热稳定性的荧光陶瓷及其制备方法 Download PDFInfo
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Abstract
一种固态照明用高显色指数高热稳定性的荧光陶瓷及其制备方法，其化学式为(Gd1‑xCex)3(Ga1‑2yCaySiy)5O12，其中x为Ce3+掺杂Gd3+位的摩尔比，y为Ca2+和Si4+分别掺杂Ga3+位的摩尔比，0.002≤x≤0.02，0≤y≤0.4。制备方法：称取氧化钆、氧化镓、氧化铈、氧化钙和二氧化硅作为原料粉体，将原料粉体、球磨介质混合球磨干燥后过筛得到混合粉体，再经干压成型、冷等静压成型得到素坯；将素坯置于真空炉中烧结、空气中退火后抛光得到荧光陶瓷。本发明制备得到的陶瓷具有热稳定性高、显色指数高、热导率高的特点，该方法使用原料种类少，烧结温度低，能有效实现陶瓷发光亮度的提升。
Description
技术领域
本发明涉及荧光陶瓷材料技术领域，具体涉及一种固态照明用高显色指数高热稳定性的荧光陶瓷及其制备方法。
背景技术
基于荧光转换型白色发光二极管(LED/LD)作为新一代的照明光源，具有发光效率高、能耗低、环保、使用寿命长等优点，目前已广泛应用于各个照明领域。
传统荧光粉与有机树脂“贴片式”封装模式的LED存在耐热性差、易老化、发光颜色不均匀等弊端，从而影响器件的使用和光参量的品质。荧光陶瓷具有良好的热学、机械以及物化稳定性，采用Ce：YAG荧光陶瓷结合远程激发的封装模式可以有效解决上述问题。然而，Ce：YAG的发射光谱中缺乏足够的红光成分，造成封装的白光LED/LD面临着显色性能较差(CRI～60)、光色品质低下等问题。
目前，国内外对LED/LD光源的光色品质的改善主要包括：(1)多色荧光材料复合，实现红、绿、黄三色耦合发光；(2)单一基质下的光谱调控，具体措施又包含基质调控以及共掺杂红光发射离子，增加红光成分。文献1(DU Q,FENG S,QIN H,et al.Massive red-shifting of Ce3+emission by Mg2+and Si4+doping of YAG:Ce transparent ceramicphosphors[J].Journal of Materials Chemistry C,2018,6.)通过Mg2+-Si4+离子对取代Ce:YAG中的Al3+-Al3+离子对，可增强红光发射，提高LED/LD光源的显色指数，但其热稳定性下降也很明显；文献2(ZHU Q Q,LI S,YUAN Q,et al.Transparent YAG:Ce ceramic withdesigned low light scattering for high-power blue LED and LD applications[J].Journal of the European Ceramic Society,2021,41(1):735-40.)通过Ce：YAG荧光粉和YAG相复合的方法制作出的Ce：YAG-YAG陶瓷实现了大功率激发照明，但其采用的烧结方式为1700℃还原气氛烧结和1650℃热等静压烧结，工艺复杂成本高，且显色指数并未有效提升。公开号为CN110218085A的发明专利公开了一种用于暖白光照明的复合荧光陶瓷的制备方法，该方法通过设计复合结构荧光陶瓷，实现了红绿黄三色耦合发光，获得了暖白光，但是其热稳定性也逐渐下降，且制造成本更高，工艺更复杂。
发明内容
本发明的目的之一是提供一种高亮度高热稳定性黄绿光荧光陶瓷，该陶瓷作为发光材料可具有热稳定性高、显色指数高、热导率高的优点。
本发明的目的之二是提供上述高亮度高热稳定性黄绿光荧光陶瓷的制备方法，该方法使用原料种类少，烧结温度低，可简化工艺和降低成本，能够有效实现陶瓷发光亮度的提升，易于实现工业化生产。
为实现上述目的，本发明采用的技术方案是：一种固态照明用高显色指数高热稳定性的荧光陶瓷，其化学式为(Gd1-xCex)3(Ga1-2yCaySiy)5O12，其中x为Ce3+掺杂Gd 3+位的摩尔比，y为Ca2+和Si4+分别掺杂Ga3+位的摩尔比，0.002≤x≤0.02，0≤y≤0.4。
本发明还提供上述固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，包括以下步骤：
(1)以氧化钆、氧化镓、氧化铈、氧化钙和二氧化硅作为原料粉体，按化学式(Gd1- xCex)3(Ga1-2yCaySiy)5O12中对应元素的化学计量比称取各原料，其中x为Ce3+掺杂Gd3+位的摩尔比，y为Ca2+和Si4+分别掺杂Ga3+位的摩尔比，0.002≤x≤0.02，0＜y≤0.4；
以氧化钆、氧化镓、氧化铈作为原料粉体，按化学式(Gd1-xCex)3Ga5O12中对应元素的化学计量比称取各原料，其中x为Ce3+掺杂Gd3+位的摩尔百分数，0.002≤x≤0.02；
(2)将上述各种原料粉体、球磨介质按一定比例混合球磨得到混合料浆，将混合料浆干燥后过筛得到混合粉体；
(3)将混合粉体放入磨具中干压成型，再进行冷等静压成型，得到相对密度为50～55％的素坯；
(4)将素坯置于真空炉中烧结得到烧结产物，烧结温度1600～1750℃，保温时间8～24h，烧结真空度不低于10-3Pa；
(5)将烧结产物在1300～1450℃的空气中退火8～24h即得到相对密度为99.5～99.9％的荧光陶瓷，最后将荧光陶瓷进行双面抛光得到高显色指数高热稳定性的荧光陶瓷。
优选的，步骤(2)中，球磨转速为180～200r/min，球磨时间为15～20h。
优选的，步骤(2)中，球磨介质是无水乙醇，所有的原料粉体与球磨介质的质量体积比为1g：(2～4)mL。
优选的，步骤(2)中，干燥温度为80～90℃，干燥时间为20～30h。
优选的，步骤(2)中，过筛的筛网目数为50～200目，过筛次数为1～3次。
优选的，步骤(3)中，所述冷等静压的保压压力为150～200Mpa，保压时间为200～400s。
优选的，步骤(4)中，真空烧结阶段的升温速率为1～10℃/min，烧结完毕后降温速率为1～10℃/min。
与现有技术方案相比，本发明具有以下优点：
(1)本发明采用Ca2+-Si4+离子对非等价取代Ga3+-Ga3+离子对，增加了离子的晶格畸变，使Ce3+离子的5d1和5d1的能级劈裂程度增大，导致Ce3+的5d1能级降低，使得Ce3+离子的电子跃迁到基态的能量相对减少，从而产生Ce3+发射光的红移，且发射峰值得到有效展宽，制备的(Gd1-xCex)3(Ga1-2yCaySiy)5O12荧光陶瓷具有优异的光学指标，并应用于固态照明；
(2)随着Ca2+-Si4+离子对掺杂量的增加，本发明制得的(Gd1-xCex)3(Ga1-2yCaySiy)5O12荧光陶瓷的发射光谱主峰在530～587nm之间，半高宽在95～130nm之间。在高功率蓝光LED(350～900mA)激发下，实现暖白光、白光或浅红光的发射，色温3500～6000K，显色指数在88～92之间；在高功率蓝光LD(2～10W)激发下，实现从暖白光、白光或浅红光的发射，色温3700～5800K，显色指数在85～90之间。当环境温度为150℃的高温时，所述荧光陶瓷的发光强度仍保持在95～98％，由此表明该荧光陶瓷具有稳定性高、显色指数高、热导率高的优点；
(3)本发明制备得到的荧光陶瓷具有热稳定性高、显色指数高、热导率高的优点；另外，该方法使用原料种类少，烧结温度低，简化工艺和降低成本，有效实现了陶瓷发光亮度的提升，易于实现工业化生产。
附图说明
图1是本发明实施例一至实施例三制得的荧光陶瓷在460nm波长激发下的发射光谱图；
图2是本发明实施例一至实施例三制得的荧光陶瓷的XRD图；
图3是本发明实施例一制得的荧光陶瓷的变温测试曲线图。
具体实施方式
以下结合附图和具体实施例对本发明作进一步详细说明。
实施例一
制备(Gd0.998Ce0.002)3Ga5O12，x＝0.002，y＝0
(1)设定目标产物质量为57.484g，按化学式(Gd0.998Ce0.002)3Ga5O12中对应元素的化学计量比称取以氧化钆(32.165g)、氧化镓(25.257g)、氧化铈(0.061g)作为原料粉体；
(2)将上述各种原料粉体、100mL无水乙醇混合球磨得到混合料浆，将混合料浆干燥后过筛得到混合粉体；球磨转速为180r/min，球磨时间为15h；干燥温度为80℃，干燥时间为20h；过筛的筛网目数为50目，过筛次数为3次；
(3)将混合粉体放入磨具中干压成型，再进行冷等静压成型，得到相对密度为50％的素坯；所述冷等静压的保压压力为150Mpa，保压时间为400s；
(4)将素坯置于真空炉中烧结得到烧结产物，烧结温度1750℃，保温时间8h，烧结真空度不低于10-3Pa；真空烧结阶段的升温速率为1℃/min，烧结完毕后降温速率为1℃/min；
(5)将烧结产物在1450℃的空气中退火24h即得到相对密度为99.9％的荧光陶瓷，最后将荧光陶瓷进行双面抛光得到高显色指数高热稳定性的荧光陶瓷。
将本实施例中得到的(Gd0.998Ce0.002)3Ga5O12荧光陶瓷进行XRD测试，结果如图2所示，从图中可以看出，所制备的材料为纯石榴石相。
本实施例中得到的(Gd0.998Ce0.002)3Ga5O12荧光陶瓷在460nm波长激发下的发射光谱图如图1所示，其发射光谱主峰为530nm，半高宽95nm。该陶瓷在高功率蓝光LED(350mA)激发下，实现暖白光发射，色温6000K，显色指数为88；在高功率蓝光LD(2W)激发下，实现暖白光发射，色温5800K，显色指数为85。
对本实施例得到的荧光陶瓷进行变温测试，结果如图3所示，从图中可以看出，当环境温度为150℃时，所述荧光陶瓷的发光强度保持在95％，由此表明该荧光陶瓷热具有稳定性高、显色指数高、热导率高的优点。
实施例二
制备化学式为(Gd0.994Ce0.006)3(Ga0.6Ca0.2Si0.2)5O12，x＝0.006，y＝0.2
(1)设定目标产物质量为58.383g，按化学式(Gd0.994Ce0.006)3(Ga0.6Ca0.2Si0.2)5O12中对应元素的化学计量比称取以氧化钆(34.471g)、氧化镓(16.306g)、氧化铈(0.197g)、氧化钙(3.576g)和二氧化硅(3.832g)作为原料粉体；
(2)将上述各种原料粉体、150mL无水乙醇混合球磨得到混合料浆，将混合料浆干燥后过筛得到混合粉体；球磨转速为190r/min，球磨时间为15h；干燥温度为90℃，干燥时间为20h；过筛的筛网目数为100目，过筛次数为2次；
(3)将混合粉体放入磨具中干压成型，再进行冷等静压成型，得到相对密度为50％的素坯；所述冷等静压的保压压力为180Mpa，保压时间为300s；
(4)将素坯置于真空炉中烧结得到烧结产物，烧结温度1650℃，保温时间16h，烧结真空度不低于10-3Pa；真空烧结阶段的升温速率为5℃/min，烧结完毕后降温速率为5℃/min；
(5)将烧结产物在1400℃的空气中退火16h即得到相对密度为99.8％的荧光陶瓷，最后将荧光陶瓷进行双面抛光得到高显色指数高热稳定性的荧光陶瓷。
将本实施例中得到的(Gd0.994Ce0.006)3(Ga0.6Ca0.2Si0.2)5O12荧光陶瓷进行XRD测试，结果如图2所示，从图中可以看出，所制备的材料为纯石榴石相。
本实施例中得到的(Gd0.994Ce0.006)3(Ga0.6Ca0.2Si0.2)5O12荧光陶瓷在460nm波长激发下的发射光谱图如图1所示，其发射光谱主峰为560nm，半高宽110nm。该陶瓷在高功率蓝光LED(600mA)激发下，实现白光的发射，色温3500K，显色指数为92；在高功率蓝光LD(8W)激发下，可实现白光发射，色温4000K，显色指数为90。当环境温度为150℃时，所述荧光陶瓷的发光强度保持在98％，由此表明该荧光陶瓷热具有稳定性高、显色指数高、热导率高的优点。
实施例三
制备化学式为(Gd0.98Ce0.02)3(Ga0.2Ca0.4Si0.4)5O12，x＝0.02，y＝0.4
(1)设定目标产物质量为59.446g，按化学式(Gd0.98Ce0.02)3(Ga0.2Ca0.4Si0.4)5O12中对应元素的化学计量比称取以氧化钆(36.802g)、氧化镓(5.886g)、氧化铈(0.713g)、氧化钙(7.746g)和二氧化硅(8.299g)作为原料粉体；
(2)将上述各种原料粉体、200mL无水乙醇混合球磨得到混合料浆，将混合料浆干燥后过筛得到混合粉体；球磨转速为200r/min，球磨时间为20h；干燥温度为90℃，干燥时间为30h；过筛的筛网目数为200目，过筛次数为1次；
(3)将混合粉体放入磨具中干压成型，再进行冷等静压成型，得到相对密度为55％的素坯；所述冷等静压的保压压力为200Mpa，保压时间为200s；
(4)将素坯置于真空炉中烧结得到烧结产物，烧结温度1600℃，保温时间24h，烧结真空度不低于10-3Pa；真空烧结阶段的升温速率为10℃/min，烧结完毕后降温速率为10℃/min；
(5)将烧结产物在1300℃的空气中退火8h即得到相对密度为99.5％的荧光陶瓷，最后将荧光陶瓷进行双面抛光得到高显色指数高热稳定性的荧光陶瓷。
将本实施例中得到的(Gd0.98Ce0.02)3(Ga0.2Ca0.4Si0.4)5O12荧光陶瓷进行XRD测试，结果如图2所示，从图中可以看出，所制备的材料为纯石榴石相。
本实施例中得到的(Gd0.98Ce0.02)3(Ga0.2Ca0.4Si0.4)5O12荧光陶瓷在460nm波长激发下的发射光谱图如图1所示，其发射光谱主峰为587nm，半高宽130nm。将该陶瓷在高功率蓝光LED(900mA)激发下，可实现浅红光发射，色温4200K，显色指数为89；在高功率蓝光LD(10W)激发下，实现浅红光发射，色温3700K，显色指数为87。当环境温度为150℃时，所述荧光陶瓷的发光强度保持在97％，由此表明该荧光陶瓷热具有稳定性高、显色指数高、热导率高的优点。
Claims (8)
1.一种固态照明用高显色指数高热稳定性的荧光陶瓷，其特征在于，其化学式为(Gd1- x Ce x )3(Ga1-2yCaySiy)5O12，其中x为Ce3+掺杂Gd 3+位的摩尔比，y为Ca2+和Si4+分别掺杂Ga3+位的摩尔比，0.002≤x≤0.02，0＜y≤0.4。
2.一种如权利要求1所述的固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，其特征在于，包括以下步骤：
（1）以氧化钆、氧化镓、氧化铈、氧化钙和二氧化硅作为原料粉体，按化学式(Gd1-x Ce x )3(Ga1-2yCaySiy)5O12中对应元素的化学计量比称取各原料，其中x为Ce3+掺杂Gd3+位的摩尔百分数，y为Ca2+和Si4+分别掺杂Ga3+位的摩尔比，0.002≤x≤0.02，0＜y≤0.4；
（2）将上述原料粉体与球磨介质按一定比例混合球磨得到混合料浆，将混合料浆干燥后过筛得到混合粉体；
（3）将混合粉体放入磨具中干压成型，再进行冷等静压成型，得到相对密度为50～55％的素坯；
（4）将素坯置于真空炉中烧结得到烧结产物，烧结温度1600～1750℃，保温时间8～24h，烧结真空度不低于10-3Pa；
（5）将烧结产物在1300~1450℃的空气中退火8~24h即得到相对密度为99.5～99.9％的荧光陶瓷，最后将荧光陶瓷进行双面抛光得到高显色指数高热稳定性的荧光陶瓷。
3.根据权利要求2所述的一种固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，其特征在于，步骤（2）中，球磨转速为180～200r/min，球磨时间为15～20h。
4.根据权利要求2或3所述的一种固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，其特征在于，步骤（2）中，球磨介质是无水乙醇，所有的原料粉体与球磨介质的质量体积比为1 g：（2～4）mL。
5.根据权利要求2或3所述的一种固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，其特征在于，步骤（2）中，干燥温度为80～90℃，干燥时间为20～30h。
6.根据权利要求2或3所述的一种固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，其特征在于，步骤（2）中，过筛的筛网目数为50～200目，过筛次数为1～3次。
7.根据权利要求2或3所述的一种固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，其特征在于，步骤（3）中，所述冷等静压的保压压力为150~200Mpa，保压时间为200~400s。
8.根据权利要求2或3所述的一种固态照明用高显色指数高热稳定性的荧光陶瓷的制备方法，其特征在于，步骤（4）中，真空烧结阶段的升温速率为1～10℃/min，烧结完毕后降温速率为1～10℃/min。
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