CN109054817A - 一种氮化物荧光物质及含有该荧光物质的发光装置 - Google Patents
一种氮化物荧光物质及含有该荧光物质的发光装置 Download PDFInfo
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Abstract
本发明属于无机发光材料技术领域,具体涉及一种氮化物荧光物质,并进一步公开一种含有该荧光物质的发光装置。本发明所述氮化物荧光物质含有如MmAlxSiyN3:aR,bEu,cCe结构的化合物,该荧光物质具有很高的物理稳定性和化学稳定性,同时该荧光物质结晶较好,因此,具有较高的外量子效率。该荧光物质应用至发光装置中时,能够充分发挥稳定性好、外量子效率高的优势,进而提高发光装置的发光效率和稳定性。
Description
技术领域
本发明属于无机发光材料技术领域,具体涉及一种氮化物荧光物质,并进一步公开一种含有该荧光物质的发光装置。
背景技术
近红外光指的是波长范围从700-1500nm的光,该波段波谱在光纤通讯、生物成像、信号转换放大等领域有着巨大应用前景,已成为国内外研究的热点。
现有近红外荧光物质基质主要采用具有石榴石结构的稀土金属氧化物,如中国专利CN101063228A、CN105733580A等公开的,或电致发光的有机配合物(Chem.-Eur.J.,2012,18,1961-1968;Adv.Mater.,2009,21,111–116;Chem.Commun.,2011,14,1833-1837;Adv.Funct.Mater.,2009,19,2639-2647)。但是由于这些已知荧光物质具有稳定性差、发光效率低等缺点,限制了该类器件在以上应用领域的应用。此外,现有技术中常见的近红外发光装置由于基本采用红外芯片,也存在着激发效率低且成本较高的问题。
因此,有必要研究开发新的荧光物质,以克服上述缺陷。
发明内容
为此,本发明所要解决的技术问题在于提供一种高亮度和高稳定性的氮化物荧光物质,以解决现有技术中荧光材料发光效率低的问题;
本发明所要解决的第二个技术问题在于提供一种含有该荧光物质的发光装置,以解决现有技术中发光装置稳定性差、发光效率低的问题。
为解决上述技术问题,本发明所述的一种氮化物荧光物质,所述荧光物质含有化学式为MmAlxSiyN3:aR,bEu,cCe的化合物,其中,
所述M元素选自Ca元素和/或Sr元素;
所述R元素选自Er元素、Nd元素、Yb元素、Cr元素、Fe元素中的至少一种;
所述参数m、x、y、a、b、c满足如下关系:0.8≤m≤1.0,0.9≤x≤1.1,0.9≤y≤1.1,0.001≤a≤0.20,0≤b≤0.20,0≤c≤0.1。
优选的,所述荧光物质具有与CaAlSiN3相同的晶体结构。
更优的,所述氮化物荧光物质中,所述M元素为Ca元素和Sr元素,且所述Ca元素占所述M元素的摩尔比不低于0.8。
作为优选,上述荧光物质的化学式中,所述参数b、c满足如下关系:0.001≤b≤0.10,0.001≤c≤0.05;
作为优选,上述荧光物质的化学式中,3≤b/c≤6。
作为优选,上述荧光物质的化学式中,所述参数x、y满足如下关系:1≤y/x≤1.3。
最优的,所述的氮化物荧光物质中,所述M元素为Ca元素,所述R元素为Er元素。
本发明所提供的氮化物荧光物质在辐射源如紫外光、蓝光芯片等的激发下,能够发出近红外光,且这种物质具有较好的发光效率,还可以大大降低成本,可用于光纤通讯、生物成像、信号转换放大和成分分析领域。
本发明提供了一种发光装置,所述发光装置至少包括所述的氮化物荧光物质以及激发光源。
优选的,所述激发光源的发射波长为360-480nm。
作为优选,所述激发光源为紫光/近紫外光半导体芯片,或蓝光半导体芯片。
更优的,所述激发光源为发射波长范围介于390-430nm的紫光/近紫外光半导体芯片,或者,所述激发光源为发射波长范围介于430-470nm的蓝光半导体芯片。
本发明所述氮化物荧光物质含有如MmAlxSiyN3:aR,bEu,cCe结构的化合物,该荧光物质具有很高的物理稳定性和化学稳定性,同时该荧光物质结晶较好,因此,具有较高的外量子效率。该荧光物质应用至发光装置中时,能够充分发挥稳定性好、外量子效率高的优势,进而提高发光装置的发光效率和稳定性。另外,选用不同稀土离子或稀土离子组合可以实现发射峰强度以及位置的可调可控,以改善其发光性能。基于上述氮化物荧光物质的特性,该荧光物质及发光装置在光纤通讯、生物成像、信号转换放大和成分分析领域具有很好的应用前景。
附图说明
为了使本发明的内容更容易被清楚的理解,下面根据本发明的具体实施例并结合附图,对本发明作进一步详细的说明,其中,
图1为采用460nm蓝光光源激发下实施例1制得的荧光物质的发射光谱图;
图2为监控波长为1538nm下实施例1制得的荧光物质的激发光谱。
具体实施方式
实施例1
以下为本发明的实施例和实施方式,只是为了说明本发明涉及的氮化物荧光物质及其发光装置,但是本发明并不局限于该实施例和实施方式。
实施例1
本实施例所述氮化物荧光物质,经过分析该荧光物质的化学式为Ca0.963AlSiN3:0.03Er,0.006Eu。
本实施例所述氮化物荧光物质,以Ca3N2、AlN、Si3N4、EuN、ErF3为原料,按照其成分为Ca0.963AlSiN3:0.03Er,0.006Eu的化学计量比,在手套箱内准确称取所述原料,并将原料放入混料罐在混料器上混合30min,取出后过筛,混合后的原料在1750℃、氮气气氛焙烧10h获得焙烧产物,焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。
利用该荧光物质封装的发光装置,激发源半导体芯片波长为460nm,其发射光谱见图1所示。从图1可以看出,该发射光谱最高峰值波长为1538nm。
该荧光物质的激发光谱如图2所示,其监控波长为1538nm,其相对强度155%,从图2可以看出,该荧光物质在250-600nm范围内能够有效激发,例如可以被近紫外光、蓝光及红光激发,具有广泛的用途。
从图1和图2结果可以看出,本实施例制得荧光物质是可在可见光激发的近红外荧光物质。
实施例2
本实施例所述氮化物荧光物质,经过分析该荧光物质的化学式为(Ca0.15,Sr0.81)AlSiN3:0.01Er,0.02Eu。
本实施例所述氮化物荧光物质,以Ca3N2、Sr2N、AlN、Si3N4、EuN、ErF3为原料,按照其成分为(Ca0.15,Sr0.81)AlSiN3:0.01Er,0.02Eu的化学计量比,在手套箱内准确称取所述原料,并将原料放入混料罐在混料器上混合30分钟,取出后过筛,混合后的原料在1800℃、氮气气氛焙烧15h获得焙烧产物,焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。将所制得荧光物质在405nm激发下,测定其发射光谱最高峰值波长为1538nm,相对强度117%。
实施例3
本实施例所述氮化物荧光物质,经过分析该荧光物质的化学式为Ca0.953AlSiN3:0.007Eu,0.03Er,0.01Ce。
本实施例所述氮化物荧光物质,以Ca3N2、Sr2N、AlN、Si3N4、EuN、ErF3、CeO2为原料,按照其成分为Ca0.953AlSiN3:0.007Eu,0.03Er,0.01Ce的化学计量比,在手套箱内准确称取所述原料,并将原料放入混料罐在混料器上混合50min,取出后过筛,混合后的原料在1700℃、氮气气氛焙烧24h获得焙烧产物,焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。
经测定,该荧光物质在405nm半导体芯片激发下,发射光谱最高峰值波长为1538nm,相对强度160%。
实施例4
本实施例所述氮化物荧光物质,经过分析该荧光物质的化学式为Ca0.899AlSiN3:0.05Yb,0.06Cr。
本实施例所述氮化物荧光物质,以Ca3N2、AlN、Si3N4、Yb2O3、Cr2O3为原料,按照其成分为Ca0.899AlSiN3:0.05Yb,0.06Cr的化学计量比,在手套箱内准确称取所述原料,并将原料放入混料罐在混料器上混合30min,取出后过筛,混合后的原料在1750℃、氮气气氛焙烧10h获得焙烧产物,焙烧产物经破碎、过筛、水洗、包膜、烘干得到所需要的荧光物质。
经测定,该荧光物质在455nm半导体芯片激发下,发射光谱呈宽带发射,发射峰位于994nm和1278nm,分别对应Cr3+和Yb3+的发射峰,发射最高峰值波长为1278nm,相对强度109%。
实施例5-22
下述实施例5-22的氮化物荧光物质,根据下表1中所示的实施例5-22通式中的化学计量比,将Ca3N2、Sr2N、AlN、Si3N4、EuN、CeO2、Nd2O3和Fe2O3在手套箱内准确称量,并将上述原料放入混料罐在混料器上混合5h,取出后过筛,混合后的原料在1800℃、氮气气氛焙烧13h获得焙烧产物,焙烧产物经破碎、过筛、水洗、包膜、烘干,即得到具有实施例5-22化学式的样品。
分别取实施例1-22的氮化物荧光物质进行光学性能测试,在460nm激发下,实施例5-22氮化物荧光物质红外区域相对强度如表1所示,以现有技术中Y2.92Al5O12:0.04Ce,0.04Nd的发光强度为100计算。
表1实施例1-22中合成的氮化物荧光物质的化学式与相对强度
发光材料化学式 | 相对强度 | |
对比例 | Y<sub>2.92</sub>Al<sub>5</sub>O<sub>12</sub>:0.04Ce,0.04Nd | 100% |
实施例1 | Ca<sub>0.963</sub>AlSiN<sub>3</sub>:0.03Er,0.006Eu | 155% |
实施例2 | (Ca<sub>0.15</sub>,Sr<sub>0.81</sub>)AlSiN<sub>3</sub>:0.01Er,0.02Eu | 117% |
实施例3 | Ca<sub>0.953</sub>AlSiN<sub>3</sub>:0.007Eu,0.03Er,0.01Ce | 160% |
实施例4 | Ca<sub>0.899</sub>AlSiN<sub>3</sub>:0.05Yb,0.06Cr | 109% |
实施例5 | CaAl<sub>0.9</sub>Si<sub>0.9</sub>N<sub>3</sub>:0.001Yb,0.2Eu,0.099Ce | 119% |
实施例6 | Ca<sub>0.8</sub>Al<sub>0.999</sub>Si<sub>1.09</sub>N<sub>3</sub>:0.001Nd,0.01Eu | 121% |
实施例7 | Ca<sub>0.99</sub>Al<sub>0.999</sub>SiN<sub>3</sub>:0.001Yb,0.01Eu | 124% |
实施例8 | CaAl<sub>0.999</sub>Si<sub>0.995</sub>N<sub>3</sub>:0.001Cr,0.01Eu | 116% |
实施例9 | Ca<sub>0.8</sub>AlSi<sub>0.945</sub>N<sub>3</sub>:0.2Fe,0.01Eu | 115% |
实施例10 | Ca<sub>0.805</sub>AlSiN<sub>3</sub>:0.03Er,0.15Eu | 114% |
实施例11 | Ca<sub>0.953</sub>Al<sub>0.9961</sub>Si<sub>0.9998</sub>N<sub>3</sub>:0.03Er,0.006Eu,0.0015Ce | 166% |
实施例12 | Ca<sub>0.155</sub>Sr<sub>0.81</sub>Al<sub>1.1</sub>Si<sub>0.9</sub>N<sub>3</sub>:0.03Er,0.04Eu | 103% |
实施例13 | Sr<sub>0.949</sub>AlSiN<sub>3</sub>:0.03Er,0.006Eu | 105% |
实施例14 | Ca<sub>0.9885</sub>AlSiN<sub>3</sub>:0.001Er,0.01Eu | 132% |
实施例15 | Ca<sub>0.9485</sub>Al<sub>0.9</sub>Si<sub>1.1</sub>N<sub>3</sub>:0.001Nd,0.001Er,0.001Yb | 113% |
实施例16 | Ca<sub>0.805</sub>AlSi<sub>1.04</sub>N<sub>3</sub>:0.03Er,0.1Eu | 131% |
实施例17 | Ca<sub>0.954</sub>AlSiN<sub>3</sub>:0.03Er,0.001Eu | 135% |
实施例18 | Ca<sub>0.9665</sub>Al<sub>0.95</sub>SiN<sub>3</sub>:0.04Er,0.003Eu,0.001Ce | 162% |
实施例19 | Ca<sub>0.954</sub>Al<sub>0.95</sub>SiN<sub>3</sub>:0.03Er,0.001Eu,0.05Ce | 136% |
实施例20 | Ca<sub>0.9685</sub>Al<sub>0.95</sub>SiN<sub>3</sub>:0.04Er,0.001Eu,0.001Ce | 157% |
实施例21 | Ca<sub>0.954</sub>Al<sub>0.9</sub>SiN<sub>3</sub>:0.03Er,0.001Eu,0.1Ce | 138% |
实施例22 | Ca<sub>0.9635</sub>Al<sub>0.95</sub>SiN<sub>3</sub>:0.04Er,0.006Eu,0.001Ce | 164% |
可见,本发明所述氮化物荧光物质具有更高的发光强度和发光性能。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种氮化物荧光物质,其特征在于,所述荧光物质含有化学式为MmAlxSiyN3:aR,bEu,cCe的化合物,其中,
所述M元素选自Ca元素和/或Sr元素;
所述R元素选自Er元素、Nd元素、Yb元素、Cr元素、Fe元素中的至少一种;
所述参数m、x、y、a、b、c满足如下关系:0.8≤m≤1.0,0.9≤x≤1.1,0.9≤y≤1.1,0.001≤a≤0.20,0≤b≤0.20,0≤c≤0.1。
2.根据权利要求1所述的氮化物荧光物质,其特征在于,所述荧光物质具有与CaAlSiN3相同的晶体结构。
3.根据权利要求1或2所述的氮化物荧光物质,其特征在于,所述M元素为Ca元素和Sr元素,且所述Ca元素占所述M元素的摩尔比不低于0.8。
4.根据权利要求1-3任一项所述的氮化物荧光物质,其特征在于,所述参数b、c满足如下关系:0.001≤b≤0.10,0.001≤c≤0.05;
优选地,3≤b/c≤6。
5.根据权利要求1-4任一项所述的氮化物荧光物质,其特征在于,所述参数x、y满足如下关系:1≤y/x≤1.3。
6.根据权利要求1-5任一项所述的氮化物荧光物质,其特征在于,所述M元素为Ca元素,所述R元素为Er元素。
7.一种发光装置,所述发光装置至少包括权利要求1-6任一项所述的氮化物荧光物质以及激发光源。
8.根据权利要求7所述的发光装置,其特征在于,所述激发光源的发射波长为360-480nm。
9.根据权利要求8所述的发光装置,其特征在于,所述激发光源为紫光/近紫外光半导体芯片,或蓝光半导体芯片。
10.根据权利要求7-9任一项所述的发光装置,其特征在于,所述激发光源为发射波长范围介于390-430nm的紫光/近紫外光半导体芯片,或者,所述激发光源为发射波长范围介于430-470nm的蓝光半导体芯片。
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