CN114836204B - 一种超宽带近红外发光材料及其制备方法和应用 - Google Patents
一种超宽带近红外发光材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种超宽带近红外发光材料及其制备方法和包含该发光材料的发光器件。化学式为La1‑zAzB1‑xNixGa11‑y‑mCryAlmO19,A包含Yb、Er、Tm、Gd、Nd、Tb、Y、Lu、Sr、Ba;B包含Mg、Zn、Ga、Al、Sc、In、Si、Ge,0<x≤0.2,0.01<y≤0.5,0≤z<1,0≤m≤11;称取元素的无机化合物,加助熔剂,研磨或搅拌再烧结,冷却后研磨,洗涤、分级得到材料,材料可应用制备近红外发光器件。本发明的近红外发光材料的量子效率高、发射光谱覆盖广,且其制备方法工艺简单,含有该发光材料的发光装置能够应用于近红外光谱技术和太阳模拟器等领域。
Description
技术领域
本发明属于发光材料技术领域,具体涉及一种超宽带近红外发光材料,特别涉及一种在可见光激发下能产生650–1700nm的近红外发光的材料,并进一步公开其制备方法,以及包含该发光材料的发光器件。
背景技术
发射光谱覆盖650–2500nm的宽带近红外光源在诸如近红外光谱技术和太阳模拟器等领域具有不可替代作用。特别是有机官能团中的含氢基团(如O-H、N-H、C-H)的振动倍频和合频在近红外区域有相应的特征吸收峰,因此,通过获取物质的近红外光谱(反射或吸收光谱)就可以分析有机物的成分与含量。近年来,随着手机、智能手表等大规模普及和多功能化,人们希望未来将传统的近红外光谱仪作为一个功能模块集成于这些便携式智能终端设备,从而实现对日常生活中食品、药物、衣物等的无损检测与即时分析,以及对人体健康状态的实时监测。作为近红外光谱技术的关键部件之一,传统的宽带近红外光源(卤钨灯、氙灯等)不但效率低、体积大、而且运行温度极高,无法满足集成化要求。此外,红外LED芯片存在发射光谱窄、成本高和光谱稳定性差等问题。采用“可见光LED+宽带近红外发光材料”的荧光转换型LED具有结构简单、效率高、成本低且光谱稳定性好等特点。开发物理化学稳定性好、外量子效率高的宽带近红外发光材料(荧光粉)对于实现荧光转换型近红外LED实用化具有重要意义。
近几年,研究人员发明了一系列宽带近红外发光材料及其LED器件。例如,中国专利CN111117618B公布了一种基于Gd3Sc2Ga3O12的Cr3+激活宽带近红外荧光粉,其发射峰值在756nm左右;中国专利CN110003909A和非专利文献Inorg.Chem.Front.,2020,7,1467公布了一种基于LaMgGa11O19的Cr3+激活宽带近红外荧光粉,其发射峰值在770nm左右;中国专利CN110079319A公布了一种混合价态红外荧光材料La2Hf2-xCrxO7-0.5x·yLaGaO3,发射峰值可以达到1200nm;中国专利CN110752283A公布了一种宽带近红外LED器件,该器件使用了Bi掺杂近红外发光玻璃。
此外,中国专利CN110093155A和非专利文献J.Mater.Chem.C,2021,9,4583-4590公布了一种基于ZnGa2O4和Zn2SnO4的Cr3+-Ni2+激活近红外二区宽带发射荧光粉,发射峰值为1330nm,内量子效率48%。但是,宽带近红外发光材料目前仍然存在着诸如量子效率低、发射带窄等问题。
发明内容
为此,本发明所要解决的技术问题在于提供一种量子效率高的超宽带近红外发光材料及其制备方法。
本发明还提供一种包含该近红外发光材料的宽带近红外发光器件,可以用于近红外光谱技术和太阳模拟器等领域。
本发明的技术方案如下:
一、一种超宽带近红外发光材料:
所述发光材料的化学式为:La1B1-xNixGa11-yCryO19、La1-zAzB1-xNixGa11-yCryO19、La1B1-xNixGa11-y-mCryAlmO19或者La1-zAzB1-xNixGa11-y-mCryAlmO19,其中,A为Yb、Er、Tm、Gd、Nd、Tb、Y、Lu、Sr和Ba的一种或其任意组合;B为Mg、Zn、Ga、Al、Sc、In、Si和Ge的一种或其任意组合,x、y、z取值范围分别为:0<x≤0.2,0.01<y≤0.5,0<z<1,0<m≤11。
所述的发光材料的主晶相具有磁铅石结构,属于六方晶系,空间群为P63/mmc。
优选的,A为Yb、Er和Tm;B为Mg、Zn和Ga;0<x≤0.05,0.1≤y≤0.3,0<z<0.5,0<m<5。
所述的发光材料在波长为380–700nm的可见光激发下,发射650–1700nm的超宽带近红外光。
本发明的超宽带是指各发射带的半高宽之和大于300nm。
所述的发光材料中,还掺杂有稀土激活离子或者惰性阳离子。
所述本发明发光材料中,通过Cr3+和Ni2+共掺杂,其中Cr3+既作为发射6500–1000发光中心,又作为Ni2+的敏化中心。
Cr3+和Ni2+共掺杂基础上,还可以添加其他稀土激活离子或者惰性阳离子实现对发光材料的发射光谱进一步调控。
二、一种超宽带近红外发光材料的制备方法,方法包括如下步骤:
按照发光材料La1-zAzB1-xNixGa11-y-mCryAlmO19中的化学计量比称取含有其中La、A、B、Ni、Ga、Cr、Al元素的高纯氧化物、碳酸盐、硝酸盐或者氟化物等无机化合物,同时加入助熔剂,充分研磨或搅拌,获得混合物;将得到的混合物进行烧结,冷却后适当研磨;最后依次经过洗涤、分级等处理即得到超宽带近红外发光材料。
所述的助熔剂采用硼酸、氟化铵、氟化锶或氟化钡等。
所述的助熔剂占据发光材料的重量百分比为1–20wt%。
所述的混合物进行烧结具体为是将混合物在1100–1500℃下在空气、氩气、氮气或氮氢混合气中烧结3–15h。
三、一种近红外发光器件,至少包含荧光转换体和激发光源,所述荧光转换体至少包括上述超宽带近红外发光材料,所述激发光源包括发光二极管LED或有机发光二极管OLED。
优选地,所述LED或OLED芯片发射380–480nm的蓝光。
例如绿色发光材料Lu3Al5O12:Ce3+和红色发光材料CaAlSiN3:Eu2+,也可以包含可被可见光或者近红外光激发的其他近红外发光材料,例如Gd3Sc1.5Al0.5Ga3O12:Cr3+、LiInSi2O6:Cr3+和Ga2O3:Cr3+;所述的荧光转换体通过将发光材料混入到环氧树脂、有机硅脂、聚碳酸酯或者低熔点玻璃等透明封装材料后固化而得。
本发明的有益效果:
本发明所述的超宽带近红外发光材料的基质材料为无机氧化物材料,其物理化学性能非常稳定。
本发明通过Cr3+到Ni2+、Yb3+、Er3+和Tm3+等的高效能量传递,可以实现在可见光激发下发射覆盖650到1700nm范围的超宽带近红外光,因而可以利用该发光材料组装成一种超宽带近红外发光装置。与现有技术相比,该发光材料的量子效率更高、光谱覆盖范围更宽,且其制备工艺简单。
附图说明
图1为本发明实施例1中近红外发光材料的XRD谱图;
图2为本发明实施例1、2、3中近红外发光材料的发射光谱图;
图3为本发明实施例1和2中近红外发光材料的激发光谱图。
具体实施方式
本发明还提供基于该近红外发光材料的一种近红外发光器件。具体地,先将近红外发光材料与有机硅脂等可以固化的透明封装材料混合得到浆料,然后涂覆在LED或者OLED芯片上,经高温固化即得所需发光器件;也可以先将该浆料单独固化成具有特定形状的荧光转换体,然后将该转换体与LED或者OLED芯片组装成发光器件;上述LED或OLED芯片的发射波长为380–480nm。
本发明近红外发光材料亦可以结合其他能够被可见光或者近红外激发的发光材料,组装成多波段发射的发光器件,从而实现具有更宽光谱覆盖范围的发光器件。
下面结合附图和具体实施例对本发明作进一步说明。
本发明的实施例如下:
实施例1
按LaMg0.98Ni0.02Ga10.8Cr0.2O19中的化学计量比,准确称取高纯的La2O3、MgO、Cr2O3、NiO和Ga2O3,以及占据LaMg0.98Ni0.02Ga10.8Cr0.2O19质量1wt%的H3BO3作为助熔剂,在玛瑙研钵中充分研磨40分钟后;将所得混合粉体于1380℃、空气中烧结6h;待自然降温后,将所得烧结产物进行研磨、洗涤、分级处理,即得到本实施例的近红外发光材料。
附图1,是本实施例样品的XRD图谱,从附图1可知,该发光材料的主晶相具有磁铅石结构,属于六方晶系,空间群为P63/mmc。
从附图2可知,该荧光粉在450nm的蓝光激发下能够发射峰值波长分别790nm和1220nm超宽带近红外光,其内量子效率大于70%。相比于对比实施例,发射光谱的波长覆盖范围显著增加。
从附图3可知,由于Cr3+到Ni2+高效能量传递实现了Ni2+在380–700nm可见光区域的有效激发,因此,可以使用发射380–700nm的LED或OLED芯片作为激发源,封装出荧光转换型发光器件。
本实施例样品在85℃/85%RH的恒温恒湿条件下进行72小时老化后,其发光强度下降幅度小于5%。
实施例2
按La0.95Er0.05Mg0.98Ni0.02Ga10.8Cr0.2O19中的化学计量比,准确称取高纯的La2O3、Er2O3、MgO、Cr2O3、NiO和Ga2O3,以及占据La0.95Er0.05Mg0.98Ni0.02Ga10.8Cr0.2O19质量3wt%的H3BO3作为助熔剂,在玛瑙研钵中充分研磨40分钟后;将所得混合粉体于1360℃、空气中烧结6h;待自然降温后,将所得烧结产物进行研磨、洗涤、分级处理,即得到本实施例的近红外发光材料。
本实施例的样品的XRD图谱与实施例1类似。从附图2可知,该荧光粉在450nm的蓝光激发下能够发射峰值波长分别790nm和1220nm以及1540nm超宽带近红外光。从附图3可知,由于Cr3+到Ni2+高效能量传递实现了Er3+在380–700nm可见光区域的有效激发。
实施例3
按La0.95Yb0.05Mg0.98Ni0.02Ga10.8Cr0.2O19中的化学计量比,准确称取高纯的La2O3、Yb2O3、MgO、Cr2O3、NiO和Ga2O3,以及占据La0.95Yb0.05Mg0.98Ni0.02Ga10.8Cr0.2O19质量3wt%的H3BO3作为助熔剂,在玛瑙研钵中充分研磨40分钟后;将所得混合粉体于1360℃、空气中烧结6h;待自然降温后,将所得烧结产物进行研磨、洗涤、分级处理,即得到本实施例的近红外发光材料。
本实施例的样品的XRD图谱与实施例1类似。从附图2可知,该荧光粉在450nm的蓝光激发下能够发射峰值波长分别790nm和1220nm以及1540nm超宽带近红外光。从附图3可知,由于Cr3+到Er3+高效能量传递实现了Er3+在380–700nm可见光区域的有效激发。
实施例4–20
实施例4–20所述的近红外发光材料,其化学式见下表1。各实施例中材料的制备方法与实施例1相似,只需根据各实施例中的化学计量比称取原料,并进行混合、研磨、烧结,其烧结温度可以做适当调整,即得到所需的近红外发光材料。对各实施例中所得的发光材料的发光性能进行表征,其结果见下表1。由表1可知,本发明所述近红外发光材料具有很宽的波长覆盖范围和波长调谐能力。
对比例
按LaMgGa10.8Cr0.2O19中的化学计量比,准确称取高纯的La2O3、MgO、Cr2O3和Ga2O3,在玛瑙研钵中充分研磨40分钟后;将所得混合粉体于1390℃、空气中烧结6h;待自然降温后,将所得烧结产物进行研磨、洗涤、分级处理,即得到所需的近红外发光材料。
表1近红外发光材料在450nm激发下的发射峰值
显然,上述实施例仅仅是为了清楚的说明所作的举例,在上述说明的基础上还可以做出其他形式的变动或变化。因此,由此所引申出的显而易见的变化或变动仍属于本发明的保护范围之内。
Claims (9)
1.一种超宽带近红外发光材料,其特征在于:
所述发光材料的化学式为:La1B1-xNixGa11-yCryO19、La1-zAzB1-xNixGa11-yCryO19、La1B1- xNixGa11-y-mCryAlmO19或者La1-zAzB1-xNixGa11-y-mCryAlmO19,其中,A为Yb、Er、Tm、Gd、Nd、Tb、Y、Lu、Sr和Ba的一种或其任意组合;B为Mg、Zn、Ga、Al、Sc、In、Si和Ge的一种或其任意组合,x、y、z取值范围分别为:0<x≤0.2,0.01<y≤0.5,0<z<1,0<m<11-0.01;
所述的发光材料的主晶相具有磁铅石结构,属于六方晶系。
2.根据权利要求1所述的超宽带近红外发光材料,其特征在于:
A为Yb、Er和Tm;B为Mg、Zn和Ga;0<x≤0.05,0.1≤y≤0.3,0<z<0.5,0<m<5。
3.根据权利要求1或2所述的超宽带近红外发光材料,其特征在于:
所述的发光材料在波长为380–700nm的可见光激发下,发射650–1700nm的超宽带近红外光。
4.应用于权利要求1–3任一所述超宽带近红外发光材料的制备方法,其特征在于方法包括如下步骤:
按照发光材料La1-zAzB1-xNixGa11-y-mCryAlmO19中的化学计量比称取含有其中La、A、B、Ni、Ga、Cr、Al元素的氧化物、碳酸盐、硝酸盐或者氟化物的无机化合物,同时加入助熔剂,充分研磨或搅拌,获得混合物;将得到的混合物进行烧结,冷却后研磨;最后依次经过洗涤、分级处理即得到超宽带近红外发光材料。
5.根据权利要求4所述的超宽带近红外发光材料的制备方法,其特征在于:
所述的助熔剂采用硼酸、氟化铵、氟化锶或氟化钡。
6.根据权利要求4所述的超宽带近红外发光材料的制备方法,其特征在于:
所述的助熔剂占据发光材料的重量百分比为1–20wt%。
7.根据权利要求4所述的超宽带近红外发光材料的制备方法,其特征在于:
所述的混合物进行烧结具体为是将混合物在1100–1500℃下在空气、氩气、氮气或氮氢混合气中烧结3–15h。
8.一种近红外发光器件,至少包含荧光转换体和激发光源,其特征在于,
所述荧光转换体至少包括权利要求1–3中任一项所述的超宽带近红外发光材料或者权利要求4-5中任一项所述制备方法制成的超宽带近红外发光材料。
9.根据权利要求8所述的发光器件,其特征在于,
所述激发光源包括发光二极管LED或有机发光二极管OLED。
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