CN112745847A - 一种钙钐锡铝石榴石基橙黄光荧光粉及其制备方法 - Google Patents

一种钙钐锡铝石榴石基橙黄光荧光粉及其制备方法 Download PDF

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CN112745847A
CN112745847A CN202110021405.3A CN202110021405A CN112745847A CN 112745847 A CN112745847 A CN 112745847A CN 202110021405 A CN202110021405 A CN 202110021405A CN 112745847 A CN112745847 A CN 112745847A
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CN112745847B (zh
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李俊豪
林利添
姜伟
倪海勇
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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Abstract

本发明公开了一种钙钐锡铝石榴石基橙黄光荧光粉及其制备方法。一种钙钐锡铝石榴石基橙黄光荧光粉,其化学组成表示式为:Ca2Sm1‑ xSn2Al3O12:xTb3+,x为掺杂的Tb3+离子浓度,其中:0.94≤x<1。本发明提出的钙钐锡铝石榴石基橙黄光荧光粉可被365‑385nm近紫外光激发,且在紫外光激发下,可发射出覆盖480‑720nm范围且绿光与红光主峰分别在543nm及616nm的橙黄色荧光。

Description

一种钙钐锡铝石榴石基橙黄光荧光粉及其制备方法
技术领域
本发明涉及发光材料技术领域,尤其涉及一种钙钐锡铝石榴石基橙黄光荧光粉及其制备方法。
背景技术
商用黄光YAG荧光粉光谱覆盖域有限,红光成分的缺失严重影响黄光YAG荧光粉在诸多功能器件中性能指标。在常见白光LED器件中,蓝光LED芯片负载单一的黄光YAG荧光粉所得到的白光显色指数偏低(Ra<80)且色温却偏高(CCT>6500K),均不利于高端场所的应用。为进一步提升LED器件的光品质,拓展其应用范畴,研制新型黄光荧光粉尤为重要。
随着半导体芯片技术的发展,在近紫外LED芯片成本造价日趋低廉的背景之下,研制与之相配的新型多光色宽覆盖域荧光粉对固态照明与显示及相关领域的产业技术升级举足轻重。使用近紫外芯片负载多色荧光粉以获得照明用LED器件或显示用LED背光源成为一种新的可能。要提高LED器件白光的显色指数和降低LED器件白光的色温,光谱当中的红光成份不可或缺。对于经典的蓝光芯片负载YAG荧光粉类型的白光LED器件,其光谱性能的改善,通常是以额外添加红光荧光粉的途径来提高红光在全光谱中的占比。但此途径有可能引入荧光粉之间的重吸收问题进而影响器件整体的发光效率,因此,当下研究倾向于在单一基质中通过发光中心的比例控制再利用共同激发或者能量传递等机制实现有效的光谱调控。
现有技术中,关于铽钐双中心共存的报道有磷酸盐基荧光粉Ba3La(PO4)3:Tb3+,Sm3 +、硅酸盐基荧光粉Ba3MgSi2O8:Tb3+,Sm3+等,但是它们在白光LED器件中的实际生产应用环节仍十分受限,主要表现在发光中心含量不够高,近紫外区域激发光利用率低,红光主峰位置不理想,因此,新型性能更优的铽钐双中心荧光粉的探寻依然任重而道远。
发明内容
本发明提供了提供了一种钙钐锡铝石榴石基橙黄光荧光粉及其制备方法,该钙钐锡铝石榴石基橙黄光荧光粉具体为橙黄光Ca2SmSn2Al3O12:Tb3+荧光粉材料(Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉),橙黄光Ca2SmSn2Al3O12:Tb3+荧光粉材料可被365-385nm近紫外光有效激发,且在近紫外光激发下,可发射出覆盖480~720nm范围且绿光与红光主峰分别在543nm及616nm的橙黄色荧光。
本发明的目的是提出了一种钙钐锡铝石榴石基橙黄光荧光粉,具体为高浓度Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光材料,其化学组成表示式为:Ca2Sm1-xSn2Al3O12:xTb3+,x为掺杂的Tb3+离子浓度,其中:0.94≤x<1。
本发明的另一个目的是提出了上述钙钐锡铝石榴石基橙黄光荧光粉的制备方法,包括如下步骤:按化学组成分别称取含有钙元素、钐元素、锡元素、铝元素和铽元素的金属元素原料,其中,金属元素物质的量之比为Ca:Sm:Sn:Al:Tb=2:(1-x):2:3:x,其中:0.94≤x<1,再加入H3BO3助熔剂于研磨容器中,充分研磨使其混合均匀,并放入反应容器中,在常压空气气氛中进行两步烧结,后冷却至室温,将产物研磨即得所述的钙钐锡铝石榴石基橙黄光荧光粉。
本发明提出的钙钐锡铝石榴石基橙黄光荧光粉利用铽桥或铽链能量传递在近紫外区域赋予基质组成Sm与被掺元素Tb高度重叠的激发光谱特性,采用高温固相法,在无特殊压强、无特定气氛要求下,直接合成得到新型的可被近紫外光有效激发的橙黄光Ca2SmSn2Al3O12:Tb3+荧光粉。
优选地,所述的含有钙元素的原料选自碳酸钙、碳酸氢钙和磷酸钙中的一种以上。
优选地,所述的含有钐元素的原料选自氧化钐、草酸钐、碳酸钐和硝酸钐中的一种以上。
优选地,所述的含有锡元素的原料选自氧化锡、草酸锡和碳酸锡中的一种以上。
优选地,所述的含有铝元素的原料选自氧化铝、氢氧化铝、碳酸铝和草酸铝中的一种以上。
优选地,所述的含有铽元素的原料选自氧化铽、草酸铽、碳酸铽和硝酸铽中的一种以上。
优选地,所述的两步烧结具体步骤为:第一步烧结温度为1450℃,时间为6h,第二步烧结温度为1550℃,烧结时间为6h。
优选地,所述的H3BO3助熔剂的物质的量的百分比为5%。所述的物质的量百分比以样品合成量(物质的量)为准来计。
本发明还保护了上述钙钐锡铝石榴石基橙黄光荧光粉在发光器件中的应用。本发明提出的橙黄光荧光粉有效激发范围宽、发射覆盖范围宽,可以应用在固态白光LED照明及显示领域当中。
与现有技术相比,本发明的有益效果是:
(1)本发明提出的高浓度Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉经两步烧结结晶性好,发光强度高,热稳定性好,显色性好,可用作暖白光LED器件的光转化层材料。
(2)该橙黄光Ca2SmSn2Al3O12:Tb3+荧光粉有效激发范围宽、发射覆盖范围宽,原料廉价易得、制造方法简单、成本低、易于工业化等优点。
(3)本发明提出的橙黄光Ca2SmSn2Al3O12:Tb3+荧光粉可被365-385nm近紫外光激发,且在紫外光激发下,可发射出覆盖480-720nm范围且绿光与红光主峰分别在543nm及616nm的橙黄色荧光,因为发射光谱覆盖天蓝、绿、橙、红、深红及远红光多个区域,且红光区域的波长、光谱比重适宜,此橙黄光对应的显色指数将更高的同时色温指标亦可有效地降低,可以应用在固态白光LED照明及显示领域当中。
附图说明
图1是实施例1制备得到的Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉的X射线粉末衍射图谱;
图2是实施例1制备得到的Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉的荧光发射光图谱;
图3是实施例1制备得到的Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉的荧光激发发射光图谱;
图4是实施例1制备得到的Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉的荧光色坐标图。
具体实施方式
以下实施例是对本发明的进一步说明,而不是对本发明的限制。除特别说明,本发明使用的设备和试剂为本技术领域常规市购产品。
实施例1
分别称取碳酸钙(CaCO3)0.2002g,氢氧化铝((Al(OH)3)0.2340g,氧化锡(SnO2)0.3014g,氧化钐(Sm2O3)0.0052g,氧化铽(Tb4O7)0.1813g,硼酸(H3BO3)0.0031g将上述原料在玛瑙研钵中研磨,研磨均匀后放入刚玉坩埚,在1450℃常压空气气氛中进行第一步烧结,恒温时间为6h,结束后取出研磨,随后在1550℃常压空气气氛中进行第二步烧结,恒温时间为6h,第二步结束后待其自然冷却,研磨均匀并获得Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉。
对得到的Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉进行测试,如图1-4所示。
实施例2
分别称取碳酸钙(CaCO3)0.2002g,氢氧化铝((Al(OH)3)0.2340g,氧化锡(SnO2)0.3014g,氧化钐(Sm2O3)0.0105g,氧化铽(Tb4O7)0.1757g,硼酸(H3BO3)0.0031g将上述原料在玛瑙研钵中研磨,研磨均匀后放入刚玉坩埚,在1450℃常压空气气氛中进行第一步烧结,恒温时间为6h,结束后取出研磨,随后在1550℃常压空气气氛中进行第二步烧结,恒温时间为6h。第二步结束后待其自然冷却,研磨均匀并获得Tb3+掺杂Ca2SmSn2Al3O12橙黄光荧光粉。
以上仅是本发明的优选实施方式,应当指出的是,上述优选实施方式不应视为对本发明的限制,本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说,在不脱离本发明的精神和范围内,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种钙钐锡铝石榴石基橙黄光荧光粉,其化学组成表示式为:Ca2Sm1-xSn2Al3O12:xTb3 +,x为掺杂的Tb3+离子浓度,其中:0.94≤x<1。
2.权利要求1所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,包括如下步骤:按化学组成分别称取含有钙元素、钐元素、锡元素、铝元素和铽元素的金属元素原料,其中,金属元素物质的量之比为Ca:Sm:Sn:Al:Tb=2:(1-x):2:3:x,其中:0.94≤x<1,再加入H3BO3助熔剂于研磨容器中,充分研磨使其混合均匀,并放入反应容器中,在常压空气气氛中进行两步烧结,后冷却至室温,将产物研磨即得所述的橙黄光Ca2SmSn2Al3O12:Tb3+荧光粉。
3.根据权利要求2所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,所述的含有钙元素的原料选自碳酸钙、碳酸氢钙和磷酸钙中的一种以上。
4.根据权利要求2所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,所述的含有钐元素的原料选自氧化钐、草酸钐、碳酸钐和硝酸钐中的一种以上。
5.根据权利要求2所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,所述的含有锡元素的原料选自氧化锡、草酸锡和碳酸锡中的一种以上。
6.根据权利要求2所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,所述的含有铝元素的原料选自氧化铝、氢氧化铝、碳酸铝和草酸铝中的一种以上。
7.根据权利要求2所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,所述的含有铽元素的原料选自氧化铽、草酸铽、碳酸铽和硝酸铽中的一种以上。
8.根据权利要求2所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,所述的两步烧结具体步骤为:第一步烧结温度为1450℃,时间为6h,第二步烧结温度为1550℃,烧结时间为6h。
9.根据权利要求2所述的钙钐锡铝石榴石基橙黄光荧光粉的制备方法,其特征在于,所述的H3BO3助熔剂的物质的量的百分比为5%。
10.权利要求1所述的钙钐锡铝石榴石基橙黄光荧光粉在发光器件中的应用。
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