CN111056847B - 一种白光led用高光效、高显指的氮氧化物荧光陶瓷及其制备方法 - Google Patents
一种白光led用高光效、高显指的氮氧化物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用高光效、高显指的氮氧化物荧光陶瓷及其制备方法,该荧光陶瓷的化学通式为:(Y1‑xCex)3Al5Li12y(O1‑yNy)12,其中,0.002≤x≤0.01,0.0<y≤0.2;将称量的初始原料、烧结助剂与无水乙醇按一定比例混合球磨,将球磨得到的混合浆料进行干燥,过筛;将过筛后的粉体进行成型,煅烧,得到陶瓷素坯,再将陶瓷素坯进行烧结,冷却到室温后进行双面抛光处理,得到所述氮氧化物荧光陶瓷。本发明首次引入共价性更强的Al3+‑N3‑键替代原有Ce:YAG陶瓷材料的Al3+‑O2‑键,实现光谱大范围红移,陶瓷的制备工艺简单,成本低。
Description
技术领域
本发明涉及一种荧光陶瓷,特别涉及一种白光LED用高光效、高显指的氮氧化物荧光陶瓷及其制备方法,属于无机发光材料技术领域。
背景技术
白光LED(white light emitting diode)作为第四代照明光源,具有低能耗、高效率、环境友好、寿命长等显著优势。当前白光LED最高效的实现方式为蓝光InGaN芯片结合稀土离子铈掺杂的钇铝石榴石(Ce:Y3Al5O12)黄色荧光粉,通过环氧树脂、硅胶等有机物封装后发射白光。然而,随着人们的照明需求不断提高,这种有机物封装荧光粉的方式已不能满足高功率高显色性能的白光LED 的需求。高功率以及高能量密度激发荧光粉将产生大量热量致使环氧树脂、硅胶等有机物加速老化从而导致白光LED的色温色坐标漂移同时使用寿命大大缩短。
Ce:YAG荧光陶瓷因具有高热导率、抗热冲击性好、光衰小等优势,能够有效替代传统“Ce:YAG荧光粉+有机树脂”技术方案,并且避免了点胶与混胶过程。然而荧光陶瓷的方案仍然有诸多问题亟需解决,其中最为突出的就是荧光光谱中缺少红光成分,从而导致的白光色温高,不柔和,并且在该方案下得到的 LED器件的发光效率和显色指数也普遍较低。
众所周知,Ce:YAG的发光特性与稀土离子Ce3+所处的晶体场强度密切相关。因此针对上述问题,研究人员针对Ce:YAG荧光陶瓷晶体结构的调整展开了相应研究。其中大部分均为具有较大离子半径的阳离子掺杂,如Gd、La、Tb等。然而该方法具有很大的局限性,同时还会导致发光离子与其他激活离子间产生能量传递导致发光强度下降并出现温度猝灭效应。但是,通过Al3+与具有更强共价性的阴离子,如N3-,形成Al3+-N3-键,从而取代Al3+-O2-键,可在保证发光效率的前提下,实现光谱的红移。由于阴离子的离子半径越大所带的负电荷越多,越容易受到阳离子极化,使得其受到的电子云膨胀效应也越强。电子云膨胀效应的增强,进一步压缩激发态d能级的位置,使发射光谱的发射峰向长波段移动(A.A. Setlur etal.Chem.Mater.20:6722(2008),US Pat.197,433)。但是,N3-引入后会导致的化学式失衡,致使样品无法形成YAG相(J.Am.Ceram,Soc,2019,DOI: 10.1111/jace.16155,金属学报,2016,52(05):607-613)。而Li+很容易与氧、氮、硫等离子化合,通过引入Li+作为电荷补偿剂,可使得化学式平衡,从而提高N3+的固溶度。
此外,Li+的偏析会对YAG晶粒的界面进行化学修饰,使晶粒尺寸发生改变,稳定晶粒界面,保证晶粒的均一生长,从而减少由于光的折射带来的量能损失,提高陶瓷的发光效率。
然而,由于在氮化物荧光粉制备过程中发光离子对晶体基质结构的要求较高,若采用传统的荧光陶瓷制备工艺,在混料和热处理时,易造成氮氧化物晶体结构缺陷和破坏,从而大幅降低发光强度。此外,传统的真空烧结以及气氛烧结通常需要在高温下长时间保温,促使取代离子更多的进入晶格。这些不利因素限制了其应用。CN106242539A通过预先使用高温固相反应法合成荧光粉,再将氮氧化物荧光粉与氧化物陶瓷粉体球磨混合,通过二次烧结制备的方法得到氮氧化物荧光陶瓷。该工艺虽然保障了氮氧化物晶体场结构,但是需要经过两步烧结,造成较大的能源消耗,并且效率低下,难以满足工业化生产以及市场化应用。
发明内容
为了克服传统Ce:YAG荧光陶瓷发射波长较短,在蓝光LED芯片的激发下色温较高,显指偏低的难题,本发明提供一种白光LED用高光效、高显指的氮氧化物荧光陶瓷。
为实现上述目的,本发明采用的技术方案如下:一种白光LED用高光效、高显指的氮氧化物荧光陶瓷,其化学通式为:
(Y1-xCex)3Al5Li12y(O1-yNy)12
其中,0.002≤x≤0.01,0.0<y≤0.2。
本发明还提供了一种上述氮氧化物荧光陶瓷的制备方法,包括以下步骤:
步骤一:按化学式(Y1-xCex)3Al5Li12y(O1-yNy)12,0.002≤x≤0.01,0.0<y≤0.2中各元素的化学计量比分别称取氧化钇、氧化铝、氧化铈、氧化锂及氮化铝,作为初始原料;
步骤二:将称量的初始原料、烧结助剂与无水乙醇置入球磨罐中,进行行星式球磨混合;
步骤三:将球磨后的混合浆料进行干燥,过筛,然后将粉体置于马弗炉中煅烧;
步骤四:将煅烧后的粉体进行干压成型,干压成型后再进行冷等静压成型,得到致密陶瓷素坯;
步骤五:将步骤四得到的陶瓷素坯进行烧结,冷却到室温后再进行双面抛光处理,得到所述氮氧化物荧光陶瓷。
优选的,步骤二中,所述球磨转速为120-160r/min,球磨时间为15-20h。
优选的,步骤二中,所述烧结助剂由占原料粉体总质量0.4-0.6%的正硅酸乙酯和0.04-0.06%的氧化镁组成,无水乙醇与原料粉体总量的质量比为1-2:1。
优选的,步骤三中,所述干燥温度为50-60℃,干燥时间为10-20h。
优选的,步骤三中,所述煅烧温度为400-900℃,升温速率为2-6℃/min,保温时间为3-6h,然后以10-30℃/min的速率降温至室温。
优选的,步骤四中,所述干压成型压力为3-9MPa,时间为180-260s;所述冷等静压成型压力为150-220MPa,保压220-360s。
优选的,步骤五中,所述烧结方式为真空烧结、热压烧结或还原气氛烧结中一种,所述烧结温度为1500-1750℃,保温8-16h。
与现有技术相比,本发明具有如下有益效果:
(1)为了调控晶体场促使发射光谱红移,本发明首次引入共价性更强的 Al3+-N3-键代替原有的Ce:YAG中的Al3+-O2-键,实现光谱大范围红移。
(2)为了平衡化学式提高N3-的固溶度,本发明通过引入Li+,作为Al3+-N3键取代Al3 +-O2-键时的补偿电荷,提高N3-的固溶度。
(3)引入Li+可以维持晶粒界面能量平衡,从而稳定晶粒生长,使得晶粒大小均一,提高陶瓷的发光效率。
(4)相较于目前已有的两步法制备氮氧化物荧光陶瓷技术,本发明采用的一步压力烧结法既保障了氮氧化物晶体场结构的稳定性,并且缩短了制备时间,减少了能耗,降低了成本。
(5)本发明提出的用于白光LED照明具有高光效、高显指的氮氧化物荧光陶瓷与蓝光芯片组装后得到的白光LED器件发光效率较高,范围在100-150 lm/W之间,显色指数可达到80-90。
附图说明
图1为本发明实施例1制备得到的氮氧化物荧光陶瓷的XRD图。
图2为本发明实施例1制备得到的氮氧化物荧光陶瓷在460nm蓝光LED芯片激发下的电致发光光谱;
图3为本发明实施例1制备得到的氮氧化物荧光陶瓷的SEM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。
以下实施例中所使用的AlN纯度>99.9%,平均粒径为2-50nm,Y2O3纯度>99.9%,平均粒径为20-100nm,CeO2纯度>99.9%,平均粒径为10-50nm, Al2O3纯度>99.9%,平均粒径为20-100nm,LiO2纯度>99.9%,平均粒径为0.1-25 nm。
实施例1
Ce:LiYAGN荧光陶瓷材料(Y0.998Ce0.002)3Al5Li0.12(O0.99N0.01)12的制备方法如下:
(1)以总量60g计,按上述化学式中各元素的化学计量比称取Y2O3:34.115 g,Al2O3:25.108g,CeO2:0.104g,AlN:0.496g,Li2O:0.181g;
(2)向称量的原料粉体中加入0.6wt.%的正硅酸乙酯和0.04wt.%的氧化镁作为烧结助剂,加入75ml无水乙醇作为介质,然后置于尼龙球磨罐中进行行星式球磨,球磨时间为15h,转速为120r/min;
(3)将球磨得到的浆料进行烘干,烘干温度为60℃,时间10h,随后过 80目筛,将过筛好的粉体在马弗炉中煅烧,升温速率为2℃/min,烧结温度为 400℃,保温时间为6h,然后以10-30℃/min的速率降温至室温;
(4)将煅烧后的粉体导入钢模中,在9MPa压强下保压260s压制成型,再进行冷等静压成型,压力为150MPa,并保压220s,得到致密陶瓷素坯;
(5)将得到的陶瓷素坯进行热压烧结,以2℃/min的升温速率升至 1600℃,保温8h,随后冷却至室温;最后将烧结好的样品进行双面抛光处理。
附图1是本实施例制备的样品的X射线衍射图谱,XRD的测试结果显示,所制备的样品的X射线衍射峰与钇铝石榴石(JCPDS(#033-0040))的标准卡片相吻合。证明了Al3+-N3-键成功取代Al3+-O2-键进入晶格中,没有导致晶格被破坏。
附图2是本实施例制备的样品在460nm蓝光激发下的电致发光光谱,可以看到。黄光区的中心波长范围位于580nm,较传统的Ce:YAG荧光陶瓷材料红移30nm,有效补充了光谱中的红光成分,显色指数为82,发光效率为122lm/W。
附图3是本实施例制备的样品的SEM图,从图中可以看出,Li+的引入可有效控制晶粒大小,减少能量损失,提高激发光的利用率。
实施例2
Ce:LiYAGN荧光陶瓷材料(Y0.996Ce0.004)3Al5Li0.36(O0.97N0.03)12的制备方法如下:
(1)以总量60g计,按上述化学式中各元素的化学计量比称取Y2O3:34.049 g,Al2O3:23.874g,CeO2:0.208g,AlN:1.489g,Li2O:0.543g;
(2)向称量的原料粉体中加入0.6wt.%的正硅酸乙酯和0.05wt.%的氧化镁作为烧结助剂,加入90ml无水乙醇作为介质,然后置于尼龙球磨罐中进行行星式球磨,球磨时间为16h,转速为130r/min;
(3)将球磨得到的浆料进行烘干,烘干温度为58℃,时间13h,随后过100目筛,将过筛好的粉体在马弗炉中煅烧,升温速率为3℃/min,烧结温度为500℃,保温时间为5h,然后以10-30℃/min的速率降温至室温;
(4)将煅烧后的粉体导入钢模中,在8MPa压强下保压240s压制成型,再进行冷等静压成型,压力为170MPa,并保压260s,得到致密陶瓷素坯;
(5)将得到的陶瓷素坯进行热压烧结,以3℃/min的升温速率升至 1500℃,保温10h,随后冷却至室温;最后将烧结好的样品进行双面抛光处理。
经过观测,本实施例2中所制备得到氮氧化物荧光陶瓷材料XRD的测试结果显示,所制备的样品的X射线衍射峰与钇铝石榴石(JCPDS(#033-0040))的标准卡片相吻合,仍为YAG相。本实施例制备的样品在458nm蓝光激发下,显色指数为84,发光效率为135lm/W。经SEM检测,可看到晶粒的大小均一。
实施例3
Ce:LiYAGN荧光陶瓷材料(Y0.994Ce0.006)3Al5Li0.6(O0.95N0.05)12的制备方法如下:
(1)以总量60g计,按上述化学式中各元素的化学计量比称取Y2O3:33.809 g,Al2O3:22.525g,CeO2:0.311g,AlN:4.118g,Li2O:0.900g;
(2)向称量的原料粉体中加入0.5wt.%的正硅酸乙酯和0.05wt.%的氧化镁作为烧结助剂,加入100ml无水乙醇作为介质,然后置于尼龙球磨罐中进行行星式球磨,球磨时间为17h,转速为140r/min;
(3)将球磨得到的浆料进行烘干,烘干温度为55℃,时间16h,随后过 150目筛。将过筛好的粉体在马弗炉中煅烧,升温速率为4℃/min,烧结温度为 600℃,保温时间为4h,然后以10-30℃/min的速率降温至室温;
(4)将煅烧后的粉体导入钢模中,在6MPa压强下保压220s压制成型,再进行冷等静压成型,压力为190MPa,并保压300s,得到致密陶瓷素坯;
(5)将得到的陶瓷素坯进行热压烧结,以4℃/min的升温速率升至 1700℃,保温12h,随后冷却至室温。最后将烧结好的样品进行双面抛光处理。
经过观测,本实施例3中所制备得到氮氧化物荧光陶瓷材料XRD的测试结果显示,所制备的样品的X射线衍射峰与钇铝石榴石(JCPDS(#033-0040))的标准卡片相吻合,仍为YAG相。本实施例制备的样品在456nm蓝光激发下,显色指数为90,发光效率为148lm/W。经SEM检测,可看到晶粒的大小均一。
实施例4
Ce:LiYAGN荧光陶瓷材料(Y0.992Ce0.008)3Al5Li1.2(O0.9N0.1)12的制备方法如下:
(1)以总量60g计,按上述化学式中各元素的化学计量比称取Y2O3:33.557 g,Al2O3:19.347g,CeO2:0.413g,AlN:4.912g,Li2O:1.791g;
(2)向称量的原料粉体中加入0.4wt.%的正硅酸乙酯和0.05wt.%的氧化镁作为烧结助剂,加入120ml无水乙醇作为介质,然后置于尼龙球磨罐中进行行星式球磨,球磨时间为18h,转速为150r/min;
(3)将球磨得到的浆料进行烘干,烘干温度为52℃,时间18h,随后过 150目筛。将过筛好的粉体在马弗炉中煅烧,升温速率为5℃/min,烧结温度为700℃,保温时间为4h,然后以10-30℃/min的速率降温至室温;
(4)将煅烧后的粉体导入钢模中,在5MPa压强下保压200s压制成型,再进行冷等静压成型,压力为200MPa,并保压330s,得到致密陶瓷素坯;
(5)将得到的陶瓷素坯进行热压烧结,以5℃/min的升温速率升至 1650℃,保温14h,随后冷却至室温。最后将烧结好的样品进行双面抛光处理。
经过观测,本实施例4中所制备得到氮氧化物荧光陶瓷材料XRD的测试结果显示,所制备的样品的X射线衍射峰与钇铝石榴石(JCPDS(#033-0040))的标准卡片相吻合,仍为YAG相。本实施例制备的样品在454nm蓝光激发下,显色指数为88,发光效率为142lm/W。经SEM检测,可看到晶粒的大小均一。
实施例5
Ce:LiYAGN荧光陶瓷材料(Y0.99Ce0.01)3Al5Li2.4(O0.8N0.2)12的制备方法如下:
(1)以总量60g计,按上述化学式中各元素的化学计量比称取Y2O3:33.144 g,Al2O3:13.101g,CeO2:0.510g,AlN:9.723g,Li2O:3.544g;
(2)向称量的原料粉体中加入0.4wt.%的正硅酸乙酯和0.06wt.%的氧化镁作为烧结助剂,加入150ml无水乙醇作为介质,然后置于尼龙球磨罐中进行行星式球磨,球磨时间为20h,转速为160r/min;
(3)将球磨得到的浆料进行烘干,烘干温度50℃,时间20h,随后过200 目筛。将过筛好的粉体在马弗炉中煅烧,升温速率为6℃/min,烧结温度为 800℃,保温时间为4h,然后以10-30℃/min的速率降温至室温;
(4)将煅烧后的粉体导入钢模中,在3MPa压强下保压180s压制成型,再进行冷等静压成型,压力为220MPa,并保压360s,得到致密陶瓷素坯;
(5)将得到的陶瓷素坯进行热压烧结,以6℃/min的升温速率升至 1750℃,保温16h,随后冷却至室温。最后将烧结好的样品进行双面抛光处理。
经过观测,本实施例5中所制备得到氮氧化物荧光陶瓷材料XRD的测试结果显示,所制备的样品的X射线衍射峰与钇铝石榴石(JCPDS(#033-0040))的标准卡片相吻合,仍为YAG相。本实施例制备的样品在450nm蓝光激发下,显色指数为84,发光效率为136lm/W。经SEM检测,可看到晶粒的大小均一。
Claims (4)
1.一种白光LED用高光效、高显指的氮氧化物荧光陶瓷的制备方法,其特征在于,包括以下步骤:
步骤一:按化学式(Y1-xCex)3Al5Li12y(O1-yNy)12,其中,0.002≤x≤0.01,0.0<y≤0.2,中各元素的化学计量比分别称取氧化钇、氧化铝、氧化铈、氧化锂及氮化铝,作为初始原料;
步骤二:向称量的原料粉体中加入占原料粉体总质量0.4-0.6%的正硅酸乙酯和占原料粉体总质量0.04-0.06%的氧化镁作为烧结助剂,加入无水乙醇作为介质,然后置于尼龙球磨罐中进行行星式球磨,球磨时间为15-20 h,转速为120-160 r/min;
步骤三:将球磨后的混合浆料进行干燥,烘干温度为50-60℃,时间10-20h,随后过筛,然后将粉体置于马弗炉中煅烧,升温速率为2-6 ℃ /min,烧结温度为400-900 ℃,保温时间为3-6 h,然后以10-30 ℃ / min的速率降温至室温;
步骤四:将煅烧后的粉体进行干压成型,干压成型后再进行冷等静压成型,再进行冷等静压成型,压力为150-220 MPa,并保压220-360 s,得到致密陶瓷素坯;
步骤五:将步骤四得到的陶瓷素坯进行热压烧结,升至1500-1750 ℃,保温8-16 h,冷却到室温后再进行双面抛光处理,得到所述氮氧化物荧光陶瓷。
2.根据权利要求1所述的白光LED用高光效、高显指的氮氧化物荧光陶瓷的制备方法,其特征在于,步骤二中,所述无水乙醇与原料粉体总量的质量比为1-2:1。
3.根据权利要求1所述的白光LED用高光效、高显指的氮氧化物荧光陶瓷的制备方法,其特征在于,步骤四中,所述干压成型压力为3-9 MPa,时间为180-260 s。
4.一种权利要求1-3任一项所述的方法获得的白光LED用高光效、高显指的氮氧化物荧光陶瓷,其特征在于,其化学通式为:
(Y1-xCex)3Al5Li12y(O1-yNy)12,
其中,0.002≤x≤0.01,0.0<y≤0.2。
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