CN106085430A - 一种上转换荧光粉及其制备方法和应用 - Google Patents

一种上转换荧光粉及其制备方法和应用 Download PDF

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CN106085430A
CN106085430A CN201610413211.7A CN201610413211A CN106085430A CN 106085430 A CN106085430 A CN 106085430A CN 201610413211 A CN201610413211 A CN 201610413211A CN 106085430 A CN106085430 A CN 106085430A
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李栋宇
黄贞
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Abstract

本发明公开了一种上转换荧光粉,化学组成通式为:Gd2‑xyz Tm x Ho y Yb z (MoO4)3,其中,Tm3+和Ho3+为激活离子;Yb3+为敏化离子;x,y,z为分别为Tm3+、Ho3+和Yb3+离子相对Gd3+离子占的摩尔百分比系数。本发明荧光粉通过钼酸根MoO4 2‑与敏化离子Yb3+ 偶合成MoO4 2‑‑Yb3+二聚物,从而对激活离子Tm3+和Ho3+实现高阶激发态能量传递上转换,降低激活离子中间能级的无辐射弛豫,提高上转换发光强度,制备工艺简单,操作安全,条件容易控制,在照明和显示领域中具有广阔的应用前景。

Description

一种上转换荧光粉及其制备方法和应用
技术领域
本发明属于上转换材料合成领域,更具体地,涉及一种上转换荧光粉及其制备方法和应用。
背景技术
利用980 nm半导体机关器来激发稀土掺杂上转换白光材料,潜在应用于白光激光器、平板显示、生物传感器、背光源和照明等,相比传统白光光源,稀土掺杂上转换白光具有无光漂白、色温易调、环保的优点,有效减少紫外污染,因此成为现在研究的热点。但是发光效率较低严重影响其应用化进程。目前公认上转换发光效率最高的基质是氟化钇钠(NaYF4),但由于在制备过程中会对环境造成一定的污染,同时热稳定性稍差。寻找一种发光强度大,热稳定性好的上转换材料尤为重要。
发明内容
本发明的目的在于提供一种上转换荧光粉。
本发明的另一目的在于提供上述荧光粉的制备方法和应用。
本发明的上述目的通过如下技术方案予以实现:
本发明提供了一种上转换荧光粉,化学组成通式为:Gd2-x-y-z Tm x Ho y Yb z (MoO4)3,其中,Tm3+和Ho3+为激活离子;Yb3+为敏化离子;x, y, z为分别为Tm3+、Ho3+和Yb3+离子相对Gd3+离子占的摩尔百分比系数,取值范围:0.001≤x≤0.02,0.001≤y≤0.02,0.01≤z≤0.20。
钼酸盐基质发光材料由于其具有良好的化学稳定性和热稳定性,而成为一类比较重要的荧光粉材料。钼酸根MoO4 2-与敏化离子Yb3+ 偶合成MoO4 2--Yb3+二聚物,从而对激活离子Tm3+和Ho3+实现高阶激发态能量传递上转换,降低激活离子中间能级的无辐射弛豫,提高上转换发光效率。
另外,钼酸盐荧光材料生产成本低,烧结温度也比其他磷酸盐、铝酸盐等体系要低,对合成过程中的降低能耗比较有利。
优选地,0.005≤x≤0.01,0.01≤y≤0.04,0.01≤z≤0.20。
上述上转换荧光粉的制备方法,包括将钆盐、钼酸盐、镱盐、钬盐在水中加热,加入柠檬酸,调节pH值,干燥,煅烧,即得所述荧光粉。
溶胶凝胶法具有制备工艺简单,易于操作,设备易得,操作安全,条件容易控制的优点。
优选地,所述制备方法为按化学组成摩尔比,将六水硝酸钆、四水钼酸铵、六水硝酸镱、六水硝酸钬,在水中混合。
优选地,所述煅烧温度为800 ℃~1000 ℃;煅烧时间为1~5小时。
优选地,所述加热温度为60~100℃。
与现有技术相比,本发明具有如下有益效果:
本发明的发光材料采用传统的溶胶凝胶法合成,制备工艺简单,易于操作,设备易得,操作安全,条件容易控制。同时实现了高激发态能量传递上转换,大大提高了上转换效率,所得荧光粉外量子效率高,增强了上转换发光。在照明和显示领域中具有广阔的应用前景。
附图说明
图1 实施例1制备得到的荧光粉材料的粉末衍射图谱。
图2实施例1制备得到的荧光粉材料的发射光谱。
图3实施例2制备得到的荧光粉材料的发射光谱。
图4实施例3制备得到的荧光粉材料的发射光谱。
图5 实施例1、2和3的色度坐标图。
具体实施方式
下面结合说明书附图和具体实施例对本发明作进一步的解释说明,但具体实施例并不对本发明作任何限定。除非特别说明,实施例中所涉及的试剂、方法均为本领域常用的试剂和方法。
实施例1:
称取六水硝酸钆(Gd(NO3)3*6H2O) 1.8750 g, 四水钼酸铵((NH4)6Mo7O24*4H2O) 1.3375g,六水硝酸镱(Yb(NO3)3*6H2O) 0.3504 g,六水硝酸铥(Tm(NO3)3*6H2O) 0.0232 g,六水硝酸钬(Ho(NO3)3*6H2O) 0.0230;溶于去离子水中并不停搅拌加热至80 °C。加入柠檬酸7.9198g继续搅拌,缓慢加入氨水,调节pH值约为7。持续搅拌半个小时,然后置于干燥箱空气气氛中130°C干燥20小时,接着放在高温箱式炉800 °C恒温2小时。自然冷却到室温。将样品取出得到产品,所得的荧光粉材料组成为:Gd1.83Tm0.01Ho0.01Yb0.15(MoO4)3
所得荧光粉材料的衍射峰位置和晶体学数据库PDF#41-1474一致,说明材料结构和基质Gd2(MoO4)3一致,见附图1。附图2为对应实例1材料的发射光谱,其荧光粉材料在980nm近红外光激发下发出强烈的上转换白光,主发射峰位置分别为476 nm、540 nm和662 nm,见附图2。利用积分球、能量计和激发光源等仪器所搭起来的量子效率测试仪,测得的外量子效率为2.10%。色坐标为(0.334,0.325),见附图5a;附图5d是标准白光点。
实施例2:
称取六水硝酸钆(Gd(NO3)3*6H2O) 1.8185 g, 四水钼酸铵((NH4)6Mo7O24*4H2O) 1.3375g,六水硝酸镱(Yb(NO3)3*6H2O) 0.3504 g,六水硝酸铥(Tm(NO3)3*6H2O) 0.0116 g,六水硝酸钬(Ho(NO3)3*6H2O) 0.0919 g;溶于去离子水中并不停搅拌加热至80 °C。加入柠檬酸7.9198g继续搅拌,缓慢加入氨水,调节pH值约为7。持续搅拌半个小时,然后置于干燥箱空气气氛中130°C干燥20小时,接着放在高温箱式炉800 °C恒温2小时。自然冷却到室温。将样品取出得到产品,所得的荧光粉材料组成为:Gd1.805Tm0.005Ho0.04Yb0.15(MoO4)3
附图3为实施例2材料的发射光谱,其荧光粉材料在980 nm近红外光激发下发出较强的上转换白光,主发射峰位置分别为476 nm、540 nm和662 nm,见附图3。测得的外量子效率为0.88%,色坐标为(0.384,0.325),见附图5b;附图5d是标准白光点。
实施例3:
称取六水硝酸钆(Gd(NO3)3*6H2O) 1.8185 g, 四水钼酸铵((NH4)6Mo7O24*4H2O) 1.3375g,六水硝酸镱(Yb(NO3)3*6H2O) 0.3504 g,六水硝酸铥(Tm(NO3)3*6H2O) 0.0116 g,六水硝酸钬(Ho(NO3)3*6H2O) 0.0919 g;溶于去离子水中并不停搅拌加热至80 °C。加入柠檬酸7.9198g继续搅拌,缓慢加入氨水,调节pH值约为7。持续搅拌半个小时,然后置于干燥箱空气气氛中130°C干燥20小时,接着放在高温箱式炉800 °C恒温2小时。自然冷却到室温。将样品取出得到产品,所得的荧光粉材料组成为:Gd1.93Tm0.01Ho0.01Yb0.05(MoO4)3
附图4为实施例3材料的发射光谱,其荧光粉材料在980 nm近红外光激发下发出较强的上转换白光,主发射峰位置分别为476 nm、540 nm和662 nm。测得的外量子效率为0.23%。色坐标为(0.421,0.320),见附图5c;附图5d是标准白光点。

Claims (7)

1.一种上转换荧光粉,其特征在于,化学组成通式为:Gd2-x-y-z Tm x Ho y Yb z (MoO4)3,其中,Tm3+和Ho3+为激活离子;Yb3+为敏化离子;x, y, z为分别为Tm3+、Ho3+和Yb3+离子相对Gd3+离子占的摩尔百分比系数,取值范围:0.001≤x≤0.02,0.001≤y≤0.02,0.01≤z≤0.20。
2.根据权利要求1所述的上转换荧光粉,其特征在于,0.005≤x≤0.01,0.01≤y≤0.04,0.01≤z≤0.20。
3.一种根据权利要求1所述的上转换荧光粉的制备方法,其特征在于,所述制备方法包括将钆盐、钼酸盐、镱盐、钬盐在水中加热,加入柠檬酸,调节pH值,干燥,煅烧,即得所述荧光粉。
4.根据权利要求3所述的制备方法,其特征在于,所述制备方法为按化学组成摩尔比,将六水硝酸钆、四水钼酸铵、六水硝酸镱、六水硝酸钬,在水中混合。
5.根据权利要求3所述的制备方法,其特征在于,所述煅烧温度为800 ℃~1000 ℃;煅烧时间为1~5小时。
6.根据权利要求3所述的制备方法,其特征在于,所述加热温度为60~100℃。
7.权利要求1或2所述的荧光粉在照明和显示领域中的应用。
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