CN116444271B - 一种ld/led用高显色指数高热稳定性荧光陶瓷及其制备方法 - Google Patents
一种ld/led用高显色指数高热稳定性荧光陶瓷及其制备方法 Download PDFInfo
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- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
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- 239000000126 substance Substances 0.000 claims abstract description 7
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- 229940093474 manganese carbonate Drugs 0.000 claims description 5
- 235000006748 manganese carbonate Nutrition 0.000 claims description 5
- 239000011656 manganese carbonate Substances 0.000 claims description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 claims description 5
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- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- 150000003624 transition metals Chemical class 0.000 description 4
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- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 3
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Abstract
本发明公开了一种LD/LED用高显色指数高热稳定性的荧光陶瓷及其制备方法。该荧光陶瓷化学式为：(Lu1‑xCex)3(Sc1‑yMny)2Al3O12，其中x为Ce3+掺杂Lu3+位的摩尔百分数，y为Mn2+掺杂Sc3+位的摩尔百分数，0.002≤x≤0.01，0.004≤y≤0.015；采用固相反应法真空烧结制得。本发明提供的荧光陶瓷发射光谱主峰在519nm～535nm之间，半高宽在110nm～125nm之间。在蓝光LD/LED(1W～5W)激发下，实现白光发射，色温3800K～6245K，显色指数在80～86之间；当环境温度为150℃时，该荧光陶瓷的发光强度保持在85％～95％，热稳定性高，且陶瓷的制备工艺简单，易于工业化生产。
Description
技术领域
本发明属于荧光陶瓷技术领域，具体涉及一种LD/LED用高显色指数高热稳定性荧光陶瓷及其制备方法。
背景技术
白光LED作为第四代照明光源，在固态照明与显示领域中已经得到了长时间的发展与应用。相比于LED，基于激光二极管(LD)的激光照明技术在高功率照明领域下仍能维持较高的发光效率，并兼具亮度更高、体积更小、寿命更长、探照距离更远等显著优势。以单颗芯片为例，蓝光LD的亮度最高是LED亮度的1000倍，耗能却只有LED的2/3，LD固态照明技术已成为照明领域的重点发展方向。
目前，白光LED/LD光源主流实现方案仍为蓝光芯片激发石榴石Y3Al5O12:Ce黄色荧光材料。相对于荧光粉，荧光陶瓷具有良好的热学、机械以及物化稳定性，但是YAG:Ce的发射光谱主要覆盖为黄绿光，缺乏足够的红光成分，因此白光LD光源也同样面临着显色性能较差(CRI～60)，色温偏高(＞6000K)，光色品质低下的难题。为了克服其本征缺陷，提高其显色性能，已有多种方案被用于调节其发光性能。主要包括：(1)设计复合结构荧光材料耦合发光。文献1利用层间成分和结构设计制备了Ce,Cr:YAG/Ce:YAG和Cr:YAG/Ce:YAG复合结构的高显色指数陶瓷。通过远程激发方式组装了陶瓷基白光LED，在460nm激发下，(Ce,Cr):YAG/Ce:YAG白光LED的CRI值达到了75.2(Huang J,Ni Y,Ma Y,et al.Compositestructure Cr:YAG/Ce:YAG and(Ce,Cr):YAG/Ce:YAG transparent ceramics with highcolor rendering index for white LEDs/LDs[J].Ceramics International,2021,47(8):11415-22.)。然而，该方法复合结构结合界面处容易导致光损耗，且制备工艺复杂，限制了其实际生活中的广泛应用。CN110218085A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。(2)离子固溶法，调节发光离子周围的晶体场环境，实现发射光谱的红移与拓宽。文献2通过共掺杂Gd3+可以使Ce3+离子的发光峰位产生红移，但是移动范围十分有限，且色温改善效果不明显(Qian X,Shi M,Yang B,et al.Thermostability and reliability propertiesstudies of transparent Ce:GdYAG ceramic by Gd substitution for white LEDs[J].Optical Materials,2019,94)。CN108264899 A公开了一种用于LED照明的多元素掺杂透明陶瓷，通过蓝光芯片激发后发出白光，但是这种陶瓷的余辉时间较长，极大的限制了其发光效率，使器件的光量损失严重。(3)红光离子掺杂，增加荧光材料的红色发光中心，弥补红光成分。文献3成功制备了Ce,Pr,Cr:YAG透明陶瓷，Pr3+离子的引用使陶瓷显色指数从50提升至72，进一步引入Cr3+将显色指数提升至78，相应CIE色坐标变为(0.35,0.40)(Feng S,Qin H,Wu G,et al.Spectrum regulation of YAG:Ce transparent ceramics with Pr,Cr doping for white light emitting diodes application[J].Journal of theEuropean Ceramic Society,2017,37(10):3403-9.)。然而，该方法对陶瓷的显色性能有限，且陶瓷的热稳定性较差。
此外，研究表明：相对于Ce:YAG而言，Ce:Lu3Al5O12荧光陶瓷的物理化学稳定性更佳，量子效率更高(在85℃、湿度85％下运行1000h后的Ce:LuAG陶瓷仍能保持其发射强度的96.6％)。可知，Ce:LuAG在热稳定性方面较有优势。然而，Ce:LuAG荧光陶瓷同样面临着红光成分缺失、相对色温较高的难题。
基于此，我们提出了LD/LED用高显色指数高热稳定性荧光陶瓷的制备方法。
发明内容
本发明的目的之一是提供LD/LED用高显色指数高热稳定性荧光陶瓷，可实现暖白光、白光发射。
本发明的目的之二是提供上述LD/LED用高显色指数高热稳定性荧光陶瓷的制备方法，易于实现工业化生产。
为了实现上述目的，本发明采用的技术方案如下：
第一方面，本发明提供一种LD/LED用高显色指数高热稳定性的荧光陶瓷，该荧光陶瓷化学式为：
(Lu1-xCex)3(Sc1-yMny)2Al3O12
其中x为Ce3+掺杂Lu3+位的摩尔百分数，y为Mn2+掺杂Sc3+位的摩尔百分数，0.002≤x≤0.01，0.004≤y≤0.015。
本发明以LuAG为基质结构，通过引入离子半径最小和电负性最大的Sc3+，成功占据了八面体Al3+位。Sc3+的引入使其最近邻键(Ce-O键)的共价键张力得以弛豫，增加了Ce3+离子所在十二面体的局部对称性，有利于陶瓷结构刚性增强，进一步提高了荧光陶瓷的热稳定性。通过引入过渡金属Mn2+离子，成功增加了在578nm处的红光发光中心，并使发射峰值得到有效展宽，有效弥补了红光成分，显著提高了荧光材料的显色指数。提供的荧光陶瓷发射光谱主峰在519nm～535nm之间，半高宽在110nm～125nm之间。在蓝光LD/LED(1W～5W)激发下，实现白光发射，色温3800K～6245K，显色指数在80～86之间。当环境温度为150℃时，所述荧光陶瓷的发光强度保持在85％～95％。
第二方面，本发明还提供上述LD/LED用高显色指数高热稳定性的荧光陶瓷的制备方法，采用固相反应法真空烧结，具体包括以下步骤：
(1)按照化学式(Lu1-xCex)3(Sc1-yMny)2Al3O12，0.002≤x≤0.01，0.004≤y≤0.015中各元素的化学计量比分别称取氧化镥、氧化铝、氧化钪、氧化铈、碳酸锰作为原料粉体；将原料粉体和球磨介质按比例混合球磨，获得混合料浆；
(2)将步骤(1)得到的混合料浆置于干燥箱中干燥，再将干燥后的混合粉体过筛；
(3)将步骤(2)过筛后的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％～60％的素坯；
(4)将步骤(3)所得素坯置于真空炉中烧结，烧结温度1700℃～1760℃，保温时间8h～24h，烧结真空度不低于10-3Pa，得到荧光陶瓷。
(5)将步骤(4)所得荧光陶瓷在空气中退火处理，退火温度1300～1450℃，保温时间8h～12h，得到相对密度为99.5％～99.9％的荧光陶瓷。
优选的，步骤(1)中，所述球磨转速为170r/min～200r/min，球磨时间为15h～24h。
优选的，步骤(1)中，所述球磨介质是无水乙醇，原料粉体与球磨介质的质量体积比为1g：2～3mL。
优选的，步骤(2)中，所述干燥时间为15h～20h，干燥温度为60℃～90℃。
优选的，步骤(2)中，所述过筛的筛网目数为80目～200目，过筛次数为1～3次。
优选的，步骤(3)中，所述冷等静压保压压力150～200MPa，保压时间200～400s。
优选的，步骤(4)中，真空烧结阶段的升温速率为1～10℃/分钟，烧结完毕后降温速率为1～10℃/分钟。
与现有技术相比，本发明具有如下有益效果：
1.本发明引入的Sc3+作为过渡离子中离子半径最小和电负性最大的离子，成功占据了八面体Al3+位。Sc3+的引入使其最近邻键(Ce-O键)的共价键张力得以弛豫，增加了Ce3+离子所在十二面体的局部对称性，有利于陶瓷结构刚性增强，显著提高了荧光陶瓷的热稳定性。
2.本发明引入过渡金属Mn2+离子，成功取代八面体Sc3+离子，并在578nm处成功增加了红色发光中心，使发射峰值得到有效展宽，有效弥补了红光成分，显著提高了荧光材料的显色指数。
3.本发明利用Ce3+的5d能级导带高于Mn2+离子的4T/4E能级导带这一特点，成功实现了Ce3+离子到过渡金属红光Mn2+离子的能量传递，使Mn2+的红色发光得以增强，调控了黄红光的颜色比例，更进一步优化了显色指数。
4.本发明基于“双离子掺杂”策略，利用Sc3+离子(微观调控Ce3+周围的环境)与过渡金属Mn2+离子(增加红光发光中心)的协同作用，成功制备了兼顾热稳定性与显色指数的高品质荧光陶瓷。
5.本发明提供的荧光陶瓷发射光谱主峰在519nm～535nm之间，半高宽在110nm～125nm之间。在蓝光LD/LED(1W～5W)激发下，实现白光发射，色温3800K～6245K，显色指数在80～86之间。当环境温度为150℃时，所述荧光陶瓷的发光强度保持在85％～95％。
附图说明
图1为本发明实施例1-3荧光陶瓷的XRD图；
图2为本发明实施例1-3荧光陶瓷的发射光谱(PL)；
图3为本发明实施例2荧光陶瓷样品的荧光变温光谱；
图4为本发明实施例2的荧光陶瓷样品在LD蓝光460nm激发下的电致发光光谱(EL)；
图5为本发明实施例3的荧光陶瓷样品在LED蓝光460nm激发下的电致发光光谱(EL)。
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99.9％。
实施例1：制备化学式为(Lu0.998Ce0.002)3(Sc0.996Mn0.004)2Al3O12的荧光陶瓷。
(1)设定目标产物质量为60.032g，按照化学式(Lu0.998Ce0.002)3(Sc0.996Mn0.004)2Al3O12中各元素的化学计量比分别称取氧化镥(40.267g)、氧化铝(10.338g)、氧化钪(9.28493g)、氧化铈(0.069g)、碳酸锰(0.062g)作为原料粉体。将原料粉体与100mL无水乙醇混合，在球磨罐中进行球磨，球磨转速为170r/min，球磨时间为15h；
(2)将步骤(1)球磨后的混和浆料置于60℃鼓风干燥箱中干燥15h，干燥后的混合粉体过80目筛，过筛2遍；
(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，成型后素坯的相对密度为50％；
(4)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24h，升温速率为1℃/分钟，烧结完毕后降温速率为1℃/分钟；陶瓷相对密度为99.5％；
(5)将烧结后的荧光陶瓷进行双面抛光至陶瓷厚度为1.0mm，得到荧光陶瓷。
将本实施例中得到的(Lu0.998Ce0.002)3(Sc0.996Mn0.004)2Al3O12荧光陶瓷进行XRD测试，结果如图1所示，表明：所制备的材料为纯石榴石相。
本实施例中得到的(Lu0.998Ce0.002)3(Sc0.996Mn0.004)2Al3O12荧光陶瓷在460nm波长激发下，其发射光谱主峰为519nm，半高宽112nm(如图2)。通过测试电致发光光谱(EL)可知，该陶瓷在LD(1W)蓝光460nm激发下，可实现显色指数为80，色温为4390K的暖白光发射；当陶瓷在LED(5W)蓝光460nm激发下时，其白光发射的显色指数为83.3，色温5186K。通过测试陶瓷的变温光谱可知，当环境温度为150℃时，所述荧光陶瓷的发光强度保持在90％。
实施例2：制备化学式为(Lu0.994Ce0.006)3(Sc0.991Mn0.009)2Al3O12的荧光陶瓷。
(1)设定目标产物质量为60.134g，按照化学式(Lu0.994Ce0.006)3(Sc0.991Mn0.009)2Al3O12中各元素的化学计量比分别称取氧化镥(40.120g)、氧化铝(10.342g)、氧化钪(9.241g)、氧化铈(0.209g)、碳酸锰(0.139g)作为原料粉体。将原料粉体与120mL无水乙醇混合，在球磨罐中进行球磨，球磨转速为190r/min，球磨时间为20h；
(2)将步骤(1)球磨后的混和浆料置于80℃鼓风干燥箱中干燥20h，干燥后的混合粉体过100目筛，过筛2遍；
(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，成型后素坯的相对密度为55％；
(4)将步骤(4)得到的陶瓷素坯放入真空炉中烧结，烧结温度为1740℃，保温时间为12h，升温速率为5℃/分钟，烧结完毕后降温速率为5℃/分钟；陶瓷相对密度为99.8％；
(5)将烧结后的荧光陶瓷进行双面抛光至陶瓷厚度为1.0mm，得到荧光陶瓷。
将本实施例中得到的(Lu0.994Ce0.006)3(Sc0.991Mn0.009)2Al3O12荧光陶瓷进行XRD测试，结果如图1所示，表明：所制备的材料为纯石榴石相。
本实施例中得到的(Lu0.994Ce0.006)3(Sc0.991Mn0.009)2Al3O12荧光陶瓷在460nm波长激发下，其发射光谱主峰为520nm，半高宽120nm(如图2)。通过测试电致发光光谱(EL)可知，该陶瓷在LD(3W)蓝光460nm激发下，可实现显色指数为80.9，色温为5316K的暖白光发射(如图4)；当陶瓷在LED(3W)蓝光460nm激发下时，其白光发射的显色指数为85，色温4263K。通过测试陶瓷的变温光谱可知(如图3)，当环境温度为150℃时，所述荧光陶瓷的发光强度保持在95％。
实施例3：制备化学式为(Lu0.99Ce0.01)3(Sc0.985Mn0.015)2Al3O12的荧光陶瓷。
(1)设定目标产物质量为60.125g，按照化学式(Lu0.99Ce0.01)3(Sc0.985Mn0.015)2Al3O12中各元素的化学计量比分别称取氧化镥(39.972g)、氧化铝(10.345g)、氧化钪(9.188g)、氧化铈(0.349g)、碳酸锰(0.233g)作为原料粉体。将原料粉体与200mL无水乙醇混合，在球磨罐中进行球磨，球磨转速为200r/min，球磨时间为24h；
(2)将步骤(1)球磨后的混和浆料置于90℃鼓风干燥箱中干燥20h，干燥后的混合粉体过200目筛，过筛1遍；
(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，成型后素坯的相对密度为60％；
(4)将步骤(4)得到的陶瓷素坯放入真空炉中烧结，烧结温度为1760℃，保温时间为8h，升温速率为10℃/分钟，烧结完毕后降温速率为10℃/分钟；陶瓷相对密度为99.9％；
(5)将烧结后的荧光陶瓷进行双面抛光至陶瓷厚度为1.0mm，得到荧光陶瓷。
将本实施例中得到的(Lu0.99Ce0.01)3(Sc0.985Mn0.015)2Al3O12荧光陶瓷进行XRD测试，结果如图1所示，表明：所制备的材料为纯石榴石相。
本实施例中得到的(Lu0.99Ce0.01)3(Sc0.985Mn0.015)2Al3O12荧光陶瓷在460nm波长激发下，其发射光谱主峰为535nm，半高宽125nm(如图2)。通过测试电致发光光谱(EL)可知，该陶瓷在LD(5W)蓝光460nm激发下，可实现显色指数为82.5，色温为6327K的暖白光发射；当陶瓷在LED(1W)蓝光460nm激发下时，其白光发射的显色指数为86，色温为6245K(如图5)。通过测试陶瓷的变温光谱可知，当环境温度为150℃时，所述荧光陶瓷的发光强度保持在85％。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种LD/LED用高显色指数高热稳定性的荧光陶瓷，其特征在于，该荧光陶瓷化学式为：
(Lu1-xCex)3(Sc1-yMny)2Al3O12
其中x为Ce3+掺杂Lu3+位的摩尔百分数，y为Mn2+掺杂Sc3+位的摩尔百分数，0.002≤x≤0.01，0.004≤y≤0.015。
2.一种权利要求1所述的LD/LED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，采用固相反应法真空烧结，具体包括以下步骤：
(1)按照化学式(Lu1-xCex)3(Sc1-yMny)2Al3O12，0.002≤x≤0.01，0.004≤y≤0.015中各元素的化学计量比分别称取氧化镥、氧化铝、氧化钪、氧化铈、碳酸锰作为原料粉体；将原料粉体和球磨介质按比例混合球磨，获得混合料浆；
(2)将步骤(1)得到的混合料浆置于干燥箱中干燥，再将干燥后的混合粉体过筛；
(3)将步骤(2)过筛后的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％～60％的素坯；
(4)将步骤(3)所得素坯置于真空炉中烧结，烧结温度1700℃～1760℃，保温时间8h～24h，烧结真空度不低于10-3Pa，得到荧光陶瓷。
(5)将步骤(4)所得荧光陶瓷在空气中退火处理，退火温度1300～1450℃，保温时间8h～12h，得到相对密度为99.5％～99.9％的荧光陶瓷。
3.根据权利要求2所述的LD/LED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(1)中，所述球磨转速为170r/min～200r/min，球磨时间为15h～24h。
4.根据权利要求2所述的LD/LED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(1)中，所述球磨介质是无水乙醇，原料粉体与球磨介质的质量体积比为1g：2～3mL。
5.根据权利要求2所述的LD/LED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，所述干燥时间为15h～20h，干燥温度为60℃～90℃。
6.根据权利要求2所述的LD/LED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，所述过筛的筛网目数为80目～200目，过筛次数为1～3次。
7.根据权利要求2所述的LD/LED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，所述冷等静压保压压力150～200MPa，保压时间200～400s。
8.根据权利要求2所述的LD/LED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℃/分钟，烧结完毕后降温速率为1～10℃/分钟。
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