CN111393166B - 一种白光led/ld用高热稳定性荧光陶瓷及其制备方法 - Google Patents
一种白光led/ld用高热稳定性荧光陶瓷及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种白光LED/LD用高热稳定性荧光陶瓷及其制备方法，该荧光陶瓷化学式为：(GdzCexY1‑x‑z)3(ScyAl1‑y)2Al3O12，其中x为Ce3+掺杂Y3+位的摩尔百分数，y为Sc3+掺杂八面体Al3+位的摩尔百分数，z为Gd3+掺杂Y3+位的摩尔百分数，0<x≤0.02，0.6≤y≤0.8，y：z＝10：1，采用固相反应法烧结制得。本发明的透明荧光陶瓷材料具有发射光谱主峰520～540nm之间，半高宽在80～90nm之间。在高功率蓝光LED(350～500mA)或蓝光LD(4W～10W)激发下，实现暖白光到淡绿光发射，色温2800～6500K，在150℃下发光强度衰减5％～10％，所制备陶瓷的工艺简单，易于工业化生产。
Description
技术领域
本发明涉及荧光陶瓷技术领域，具体涉及一种白光LED/LD用高热稳定性荧光陶瓷及其制备方法。
背景技术
能源危机、气候变暖、生态环境污染等全球问题使环保节能产业广受国内外的重视。在半导体照明领域，白光LED作为新一代绿色固态照明光源，因其发光效率高、器件体积小、使用寿命长等诸多优点，具有无与伦比的竞争优势。随着社会的发展及生活品质的提高，人们更加热衷于追求高功率高品质健康绿色照明光源。所以，传统的将荧光粉Ce3+:Y3Al5O12(Ce:YAG)与有机硅胶混合的方式正逐步被芯片接合Ce:YAG荧光陶瓷的远程激发封装方式所取代。作为新型白光LED的核心材料之一，荧光陶瓷以其导热系数高、机械性能好、易实现高掺杂浓度等优点成为主流发展对象及国内外研究的热点。然而，在蓝光LED/LD激发下，Ce:YAG荧光陶瓷发射出的光颜色比例失调及热猝灭，导致制备的照明器件显色指数偏低、相对色温偏高、光效低等缺陷，无法满足使用要求。为了解决上述难题，必须要对Ce:YAG荧光陶瓷进行改性。虽然已有多篇关于关于铈掺杂钇铝石榴石、镥铝石榴石、钆铝石榴石的文献报道。但是，由于在调控光谱的同时，荧光陶瓷的热稳定性随之下降，即，在正常服役温度环境下，发光强度大都下降至50％以下。
目前国内外调控荧光陶瓷光谱的方法主要分为增加红光离子(J.Eur.Ceram.Soc.,2017,37(10),3403–3409.)，通过调控能级来增加发射光谱半高宽(ACS Appl.Mater.Interfaces,2019,11(2),2130–2139.)，复合结构实现红、绿、黄三色耦合发光(CN110218085A)。上述方法有自个优点，但是缺陷也比较明显，即荧光陶瓷的热稳定性变差，极易发生温度猝灭。
发明内容
本发明的目的之一是提供一种白光LED/LD用高热稳定性荧光陶瓷，热稳定性好。
本发明的目的之二是提供上述白光LED/LD用高热稳定性荧光陶瓷的制备方法，易于(半)工业化生产。
为实现上述目的，本发明采用的技术方案如下：一种白光LED/LD用高热稳定性荧光陶瓷，该荧光陶瓷化学式为：
(GdzCexY1-x-z)3(ScyAl1-y)2Al3O12
其中x为Ce3+掺杂Y3+位的摩尔百分数，y为Sc3+掺杂八面体Al3+位的摩尔百分数，z为Gd3+掺杂Y3+位的摩尔百分数，0<x≤0.02，0.6≤y≤0.8，y：z＝10：1。
在高功率蓝光LED(350～500mA)或蓝光LD(4W～10W)激发下，实现暖白光到淡绿光发射，色温2800～6500K。且随着温度增加，该荧光陶瓷的发光强度逐渐降低，但是在室温～150℃范围内，发光强度随温度升高降低不明显，150℃时发光强度衰减5％～10％，热稳定性好。
本发明还提供上述白光LED/LD用高热稳定性荧光陶瓷的制备方法，采用固相反应法烧结，具体包括以下步骤：
(1)按照化学式(GdzCexY1-x-z)3(ScyAl1-y)2Al3O12，0<x≤0.02，0.6≤y≤0.8，y：z＝10：1，中各元素的化学计量比分别称取α-氧化铝、氧化钇、氧化钆、氧化钪和氧化铈作为原料粉体；将原料粉体、电荷补偿剂、分散剂、球磨介质按一定比例混合球磨，获得混合料浆；
(2)将步骤(1)得到的混合料浆置于烘箱中干燥，再将干燥后的混合粉体过筛后置于600℃～700℃条件下煅烧除杂；
(3)将步骤(2)煅烧后的粉体放入磨具中干压成型后再进行冷等静压成型，得到相对密度为52％～53％的素坯；
(4)将步骤(3)所得素坯先置于管式炉中预烧，烧结温度为600℃～900℃，保温时间为2h～4h，而后置于真空炉中烧结，烧结温度1700℃～1750℃，保温时间4h～15h，烧结真空度不低于10-3Pa，得到荧光陶瓷；
(5)将步骤(4)真空烧结后的荧光陶瓷进行空气退火处理，退火温度1100℃～1250℃，保温时间为20h～50h，得到相对密度为99％～99.9％的高热稳定性荧光陶瓷。
优选的，步骤(1)中，所述电荷补偿剂为正硅酸乙酯，其加入量为铈源的1wt.％～2wt.％。
优选的，步骤(1)中，所述分散剂为聚醚酰亚胺，其加入量为铈源的5wt.％～10wt.％。
优选的，步骤(1)中，所述球磨转速为180r/min～200r/min，球磨时间为20h～25h。
优选的，步骤(2)中，所述干燥时间为10h～20h，干燥温度为50℃～60℃。
优选的，步骤(2)中，所述煅烧时间为4h～6h。
优选的，步骤(4)中，管式炉预烧阶段的升温速率为1～2℃/分钟，烧结完毕后降温速率为1～2℃/分钟；真空烧结阶段的升温速率为0.5～1℃/分钟，烧结完毕后降温速率为1～2℃/分钟。
与现有技术相比，本发明具有如下有益效果：
1.本发明提供的荧光陶瓷采用电负性最大、半径最小的稀土元素Sc取代八面体Al格位，Gd3+离子取代十二面体Y3+离子。充分利用处于八面体格位的Sc3+离子和处于十二面体格位Gd3+形成离子对匹配效应，消除晶格畸变，提高Ce3+离子发光热稳定性，同时利用八面体格位的Sc3+离子调控斯托克斯位移和光谱位置，最大程度改善发射光颜色。两者协同效应提升荧光陶瓷在高功率下的服役性能。
2.本发明通过固相反应法获得了纯石榴石相的荧光陶瓷。通过控制化学配比，使Sc3+离子(半径为0.0885nm,CN＝6)只占据八面体Al3+离子(半径为0.0675nm,CN＝6)格位，实施例的XRD及SEM检测结果显示没有发现第二相的存在，生成陶瓷是纯相。
3.本发明提供的荧光陶瓷可以有效地解决荧光陶瓷中青绿光不足问题，可有效提高LED/LD器件显色指数，得到低色温的白光。在高功率蓝光LED(350～500mA)或蓝光LD(4W～10W)的激发下，发射光谱主峰520～540nm之间，半高宽在80～90nm之间，实现暖白光到淡绿光发射，色温2800～6500K。
4.本发明提供的荧光陶瓷在150℃下发光强度衰减5％～10％，热稳定性好。
附图说明
图1为本发明实施例3制得荧光陶瓷在460nm波长激发下的发射光谱；
图2为本发明实施例3制得荧光陶瓷的透过率图；
图3为本发明实施例3制得荧光陶瓷随温度变化的发射光谱图；
图4为本发明实施例1至4制得荧光陶瓷的XRD图；
图5为本发明实施例3制得荧光陶瓷表面SEM图；
图6为本发明实施例1至4制得荧光陶瓷的实物图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
以下实施例中使用的原料粉体均为市售商品，纯度均大于99.99％，所述α相氧化铝平均粒径250nm～300nm；所述氧化钇平均粒径10nm～100nm；所述氧化钆平均粒径10nm～100nm；所述氧化钪平均粒径50nm～100nm；所述氧化铈平均粒径10nm～50nm。
实施例1：制备化学式为(Gd0.06Y0.938Ce0.002)3(Al0.4Sc0.6)2Al3O12荧光陶瓷
(1)设定目标产物质量为60g，按照化学式(Gd0.06Y0.938Ce0.002)3(Al0.4Sc0.6)2Al3O12中各元素的化学计量比分别称取氧化铝(18.515g)、氧化钇(30.365g)、氧化钆(3.118g)、氧化钪(7.908g)和氧化铈(0.99g)作为原料粉体；将原料粉体、0.00156g正硅酸乙酯、0.0078gPEI、120ml无水乙醇混合，加入直径为1mm氧化铝球120g，在氧化铝球磨罐中进行球磨，球磨转速为180r/min，球磨时间为25h；
(2)将步骤(1)球磨后的混和浆料置于50℃鼓风干燥箱中干燥10h，干燥后的混合粉体过80目筛，过筛5遍，然后在空气气氛下煅烧除去残留有机物，煅烧温度600℃，煅烧时间4h；
(3)将步骤(2)煅烧后的粉体放入磨具中干压成型后再进行冷等静压成型，所述冷等静压的压力为220MPa，保压时间为500s，成型后素坯的相对密度为52％；
(4)将成型后素坯在管式炉下煅烧，煅烧温度600℃，煅烧时间2h，升温速率为1℃/分钟，烧结完毕后降温速率为1℃/分钟；
(5)将步骤(4)得到的陶瓷素坯放入真空炉中烧结，烧结温度为1700℃，保温时间为4h，升温速率为0.5℃/分钟，烧结完毕后降温速率为1℃/分钟；
(6)将步骤(5)得到的陶瓷放入马弗炉中退火，退火温度1100℃，保温时间为20h，陶瓷相对密度为99％。
将烧结后的透明陶瓷进行双面抛光至陶瓷厚度为1.0mm，得到高热稳定性荧光陶瓷，其实物为黄色透明陶瓷(如图6中编号1)。
将本实施例中得到的(Gd0.06Y0.938Ce0.002)3(Al0.4Sc0.6)2Al3O12荧光陶瓷进行XRD测试，测试结果如图4所示，表明：所制备的材料为纯石榴石相。
将本实施例中得到的(Gd0.06Y0.938Ce0.002)3(Al0.4Sc0.6)2Al3O12荧光陶瓷在460nm波长的蓝光LED芯片(I＝350mA)激发下进行发射光谱测试，其发射光谱主峰534nm，半高宽88.3nm，实现淡绿光发射，色温4000K。
将本实施例得到的(Gd0.06Y0.938Ce0.002)3(Al0.4Sc0.6)2Al3O12荧光陶瓷进行随温度变化的发射光谱测试。结果表明：随着温度增加，陶瓷的发光强度逐渐降低，但是在室温～150℃范围内，发光强度随温度升高降低不明显，150℃时发光强度仅降低9.7％。
将本实施例中得到的(Gd0.06Y0.938Ce0.002)3(Al0.4Sc0.6)2Al3O12荧光陶瓷进行透过率测试，结果表明：该荧光陶瓷透过率T＝59.64％@800nm。
实施例2：制备化学式为(Gd0.07Y0.928Ce0.002)3(Al0.3Sc0.7)2Al3O12荧光陶瓷
(1)设定目标产物质量为60g，按照化学式中各元素的化学计量比分别称取氧化铝(17.384g)、氧化钇(29.773g)、氧化钆(3.605g)、氧化钪(9.144g)和氧化铈(0.098g)作为原料粉体；将原料粉体、0.00234g正硅酸乙酯、0.00936gPEI、130ml无水乙醇混合，加入直径为2mm氧化铝球150g，在氧化铝球磨罐中进行球磨，球磨转速为190r/min，球磨时间为22h；
(2)将步骤(1)球磨后的混和浆料置于55℃鼓风干燥箱中干燥15h，干燥后的混合粉体过90目筛，过筛4遍，然后在空气气氛下煅烧除去残留有机物，煅烧温度650℃，煅烧时间5h；
(3)将步骤(2)煅烧后的粉体放入磨具中干压成型后再进行冷等静压成型；所述冷等静压的压力为220MPa，保压时间为500s，成型后素坯的相对密度为52.5％；
(4)将成型后素坯在管式炉下煅烧，煅烧温度650℃，煅烧时间3h，升温速率为1℃/分钟，烧结完毕后降温速率为1℃/分钟；
(5)将步骤(4)得到的陶瓷素坯放入真空炉烧结，烧结温度为1720℃，保温时间为8h，升温速率为0.8℃/分钟，烧结完毕后降温速率为1.5℃/分钟；
(6)将步骤(5)得到的陶瓷放入马弗炉中退火，退火温度1200℃，保温时间为30h，陶瓷相对密度为99.5％。
将烧结后的透明陶瓷进行双面抛光至陶瓷厚度为1.0mm，得到高热稳定性LED/LD照明用荧光陶瓷，其实物为淡黄色透明陶瓷(如图6中编号2)。
将本实施例中得到的(Gd0.07Y0.928Ce0.002)3(Al0.3Sc0.7)2Al3O12荧光陶瓷进行XRD测试，测试结果如图4所示，表明：所制备的材料为纯石榴石相。
将本实施例中得到的(Gd0.07Y0.928Ce0.002)3(Al0.3Sc0.7)2Al3O12荧光陶瓷在460nm波长的蓝光LED芯片(I＝350mA)激发下进行发射光谱测试，结果表明：发射光谱主峰531nm，半高宽84.2nm，实现淡绿色光发射，色温4500K。
将本实施例得到的(Gd0.07Y0.928Ce0.002)3(Al0.3Sc0.7)2Al3O12荧光陶瓷进行随温度变化的发射光谱测试。结果表明：随着温度增加，陶瓷的发光强度逐渐降低，但是在室温～150℃范围内，发光强度随温度升高降低不明显，150℃时发光强度仅降低6.8％。
将本实施例中得到的(Gd0.07Y0.928Ce0.002)3(Al0.3Sc0.7)2Al3O12荧光陶瓷进行透过率测试，结果表明：该荧光陶瓷透过率T＝66.93％@800nm。
实施例3：制备化学式为(Gd0.075Y0.922Ce0.003)3(Al0.25Sc0.75)2Al3O12荧光陶瓷
(1)设定目标产物质量为60g，按照化学式中各元素的化学计量比分别称取氧化铝(16.822g)、氧化钇(29.442g)、氧化钆(3.845g)、氧化钪(9.751g)和氧化铈(0.146g)作为原料粉体；将原料粉体、0.00312g正硅酸乙酯、0.0156gPEI、150ml无水乙醇混合，加入直径为5mm氧化铝球180g，在氧化铝球磨罐中进行球磨，球磨转速为200r/min，球磨时间为25h；
(2)将步骤(1)球磨后的混和浆料置于60℃鼓风干燥箱中干燥20h，干燥后的混合粉体过100目筛，过筛3遍，然后在空气气氛下煅烧除去残留有机物，煅烧温度700℃，煅烧时间6h；
(3)将步骤(2)煅烧后的粉体放入磨具中干压成型后再进行冷等静压成型；所述冷等静压的压力为220MPa，保压时间为500s，成型后素坯的相对密度为53％；
(4)将成型后素坯在管式炉下煅烧，煅烧温度900℃，煅烧时间4h，升温速率为2℃/分钟，烧结完毕后降温速率为2℃/分钟；
(5)将步骤(4)得到的陶瓷素坯放入真空炉烧结，烧结温度为1750℃，保温时间为15h，升温速率为1℃/分钟，烧结完毕后降温速率为2℃/分钟；
(6)将步骤(5)得到的陶瓷放入马弗炉中退火，退火温度1250℃，保温时间为50h，陶瓷相对密度为99.9％。
将烧结后的透明陶瓷进行双面抛光至陶瓷厚度为1.0mm，得到高热稳定性LED/LD照明用荧光陶瓷，其实物为淡绿色透明陶瓷(如图6中编号3)。
将本实施例中得到的(Gd0.075Y0.922Ce0.003)3(Al0.25Sc0.75)2Al3O12荧光陶瓷进行XRD测试，测试结果如图4所示，表明：所制备的材料为纯石榴石相。
将本实施例中得到的(Gd0.075Y0.922Ce0.003)3(Al0.25Sc0.75)2Al3O12荧光陶瓷进行表面SEM测试，测试结果如图5所示，表明：所制备的材料晶粒尺寸均一且晶界干净，无杂相。
将本实施例中得到的(Gd0.075Y0.922Ce0.003)3(Al0.25Sc0.75)2Al3O12荧光陶瓷在460nm波长的蓝光LED芯片(I＝500mA)激发下进行发射光谱测试，结果如图1所示，表明：发射光谱主峰526nm，半高宽83.7nm，实现淡绿色发射，色温5945K。
将本实施例中得到的(Gd0.075Y0.922Ce0.003)3(Al0.25Sc0.75)2Al3O12荧光陶瓷进行透过率测试，结果如图2所示，表明：该荧光陶瓷透过率T＝72.41％@800nm。
图3为本实施例得到的(Gd0.075Y0.922Ce0.003)3(Al0.25Sc0.75)2Al3O12荧光陶瓷随温度变化的发射光谱图。结果表明：随着温度增加，陶瓷的发光强度逐渐降低，但是在室温～150℃范围内，发光强度随温度升高降低不明显，150℃时发光强度仅降低6.0％。
实施例4：制备化学式为(Gd0.08Y0.9Ce0.02)3(Al0.2Sc0.8)2Al3O12荧光陶瓷
(1)设定目标产物质量为60g，按照化学式中各元素的化学计量比分别称取氧化铝(16.203g)、氧化钇(28.534g)、氧化钆(4.066g)、氧化钪(10.313g)和氧化铈(0.965g)作为原料粉体；将原料粉体、0.0028g正硅酸乙酯、0.01248gPEI、160ml无水乙醇混合，加入直径为2mm氧化铝球170g，在氧化铝球磨罐中进行球磨，球磨转速为195r/min，球磨时间为24h；
(2)将步骤(1)球磨后的混和浆料置于58℃鼓风干燥箱中干燥16h，干燥后的混合粉体过90目筛，过筛4遍，然后在空气气氛下煅烧除去残留有机物，煅烧温度660℃，煅烧时间6h；
(3)将步骤(2)煅烧后的粉体放入磨具中干压成型后再进行冷等静压成型；所述冷等静压的压力为220MPa，保压时间为500s，成型后素坯的相对密度为52.8％；
(4)将成型后素坯在管式炉下煅烧，煅烧温度800℃，煅烧时间3h，升温速率为2℃/分钟，烧结完毕后降温速率为2℃/分钟；
(5)将步骤(4)得到的陶瓷素坯放入真空炉烧结，烧结温度为1740℃，保温时间为10h，升温速率为0.8℃/分钟，烧结完毕后降温速率为1.8℃/分钟；
(6)将步骤(5)得到的陶瓷放入马弗炉中退火，退火温度1150℃，保温时间为40h，陶瓷相对密度为99.7％。
将烧结后的透明陶瓷进行双面抛光至陶瓷厚度为1.0mm，得到高热稳定性LED/LD照明用荧光陶瓷，其实物为淡绿色透明陶瓷(如图6中编号4)。
将本实施例中得到的(Gd0.08Y0.9Ce0.02)3(Al0.2Sc0.8)2Al3O12荧光陶瓷进行XRD测试，测试结果如图4所示，表明：所制备的材料为纯石榴石相。
将本实施例中得到的(Gd0.08Y0.9Ce0.02)3(Al0.2Sc0.8)2Al3O12荧光陶瓷在460nm波长的蓝光LED芯片(I＝400mA)激发下进行发射光谱测试，结果表明：发射光谱主峰535nm，半高宽81.0nm，实现暖白光发射，色温3400K。
将本实施例得到的(Gd0.08Y0.9Ce0.02)3(Al0.2Sc0.8)2Al3O12荧光陶瓷进行随温度变化的发射光谱测试。结果表明：随着温度增加，陶瓷的发光强度逐渐降低，但是在室温～150℃范围内，发光强度随温度升高降低不明显，150℃时发光强度仅降低9.5％。
将本实施例中得到的(Gd0.08Y0.9Ce0.02)3(Al0.2Sc0.8)2Al3O12荧光陶瓷进行透过率测试，结果表明：该荧光陶瓷透过率T＝56.32％@800nm。
Claims (7)
1.一种白光LED或白光LD用高热稳定性荧光陶瓷，其特征在于，该荧光陶瓷化学式为：
(GdzCexY1-x-z)3(ScyAl1-y)2Al3O12
其中x为Ce3+掺杂Y3+位的摩尔百分数，y为Sc3+掺杂八面体Al3+位的摩尔百分数，z为Gd3+掺杂Y3+位的摩尔百分数，0<x≤0.02，0.6≤y≤0.8，y：z＝10：1；
当环境温度为150℃时，所述荧光陶瓷的发光强度衰减5％～10％。
2.一种权利要求1所述的白光LED或白光LD用高热稳定性荧光陶瓷的制备方法，其特征在于，采用固相反应法烧结，具体包括以下步骤：
(1)按照化学式(GdzCexY1-x-z)3(ScyAl1-y)2Al3O12，0<x≤0.02，0.6≤y≤0.8，y：z＝10：1中各元素的化学计量比分别称取α-氧化铝、氧化钇、氧化钆、氧化钪和氧化铈作为原料粉体；将原料粉体、电荷补偿剂、分散剂、球磨介质按一定比例混合球磨，获得混合料浆，所述电荷补偿剂为正硅酸乙酯，其加入量为铈源的1wt.％～2wt.％；
(2)将步骤(1)得到的混合料浆置于干燥箱中干燥，再将干燥后的混合粉体过筛后置于600℃～700℃条件下煅烧除杂；
(3)将步骤(2)煅烧后的粉体放入磨具中干压成型后再进行冷等静压成型，得到相对密度为52％～53％的素坯；
(4)将步骤(3)所得素坯先置于管式炉中预烧，烧结温度为600℃～900℃，保温时间为2h～4h，而后置于真空炉中烧结，烧结温度1700℃～1750℃，保温时间4h～15h，烧结真空度不低于10-3Pa，得到荧光陶瓷；
(5)将步骤(4)真空烧结后的荧光陶瓷进行空气退火处理，退火温度1100℃～1250℃，保温时间为20h～50h，得到相对密度为99％～99.9％的高热稳定性荧光陶瓷。
3.根据权利要求2所述的白光LED或白光LD用高热稳定性荧光陶瓷的制备方法，其特征在于，步骤(1)中，所述分散剂为聚醚酰亚胺，其加入量为铈源的5wt.％～10wt.％。
4.根据权利要求2所述的白光LED或白光LD用高热稳定性荧光陶瓷的制备方法，其特征在于，步骤(1)中，所述球磨转速为180r/min～200r/min，球磨时间为20h～25h。
5.根据权利要求2所述的白光LED或白光LD用高热稳定性荧光陶瓷的制备方法，其特征在于，步骤(2)中，所述干燥时间为10h～20h，干燥温度为50℃～60℃。
6.根据权利要求2所述的白光LED或白光LD用高热稳定性荧光陶瓷的制备方法，其特征在于，步骤(2)中，所述煅烧时间为4h～6h。
7.根据权利要求2所述的白光LED或白光LD用高热稳定性荧光陶瓷的制备方法，其特征在于，步骤(4)中，管式炉预烧阶段的升温速率为1～2℃/分钟，烧结完毕后降温速率为1～2℃/分钟；真空烧结阶段的升温速率为0.5～1℃/分钟，烧结完毕后降温速率为1～2℃/分钟。
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