CN113736462B - 一种氮氧化物荧光材料及其制备方法和应用 - Google Patents
一种氮氧化物荧光材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种氮氧化物荧光材料及其制备方法和应用,所述氮氧化物荧光材料的分子式为La1‑x‑yEuyCaxSiO2+xN1‑x,其中,0≤x<1,0<y≤0.1,所述氮氧化物荧光材料的基质中固溶激活剂Eu而被激活,从而具有发光特性。所述氮氧化物荧光材料是由La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体、Eu2O3和/或EuF3和/或EuCl2粉体混合后,在氮气‑氢气混合气氛或者氮气‑氢气‑氨气混合气氛下、于1300~1550℃温度范围保温烧结得到。所述氮氧化物荧光材料被紫外光激发后,可调控地发射出蓝光、绿光、黄光系列荧光,量子产率高,在照明领域具有较好的应用前景。
Description
技术领域
本发明涉及荧光材料,尤其是一种氮氧化物荧光材料及其制备方法和应用。
背景技术
稀土Eu2+掺杂荧光材料的光学性能与荧光材料基质的晶体结构,尤其与稀土离子的局域配位结构,直接相关。通常,材料晶体结构的确认依赖于实验和计算两个方面。从实验层面上讲,可以通过解析X射线衍射数据确认材料的晶体结构。从理论计算层面上讲,可以基于密度泛函理论(DFT)计算构建材料的晶体结构。La-Si-O-N材料体系,包括LaSiO2N,La5Si3O12N,La4Si2O7N2,La2Si6O3N8等被作为典型荧光材料体系得到广泛的研究。然而,长久以来关于LaSiO2N的晶体结构的研究一直争议不断,目前文献中都将其晶体结构默认为无机晶体结构数据库(ICSD)中的六方晶系,空间群为P-6c2,参见非专利文献1(MorganP.E.D,et al“Journal of Materials Science”1977;12:2343-2344),然而,在该晶体结构中,La存在2种配位结构,LaO6和LaO6N6,即N原子存在明显富集现象,从能量最低角度,ICSD中六方的LaSiO2N的结构模型是不稳定的。LaSiO2N晶体结构的确定对于研究其稀土掺杂的光学性能十分重要。此外,在Eu掺杂LaSiO2N荧光材料中,由于Eu2+和La3+价态不匹配,通常会存在Eu2+和Eu3+共存的现象,Eu3+的存在导致发光材料性能不佳,参见非专利文献2(ChenJ,et al“ScientificReports”2016;6:31199)。
发明内容
本发明的目的是为了克服现有的La-Si-O-N材料体系中晶体结构存在不确定性、材料量子产率低的技术问题,提供一种氮氧化物荧光材料,其分子式为La1-x-yEuyCaxSiO2+ xN1-x(0≤x<1,0<y≤0.1),其中La1-x-yEuyCaxSiO2+xN1-x(0≤x≤0.1,0<y≤0.1)的空间群为C2/c,晶体结构与LaSiO2N相同;La1-x-yEuyCaxSiO2+xN1-x(0.1<x≤0.7,0<y≤0.1)的空间群为P63/m,晶体结构与La5Si3O12N相同;La1-x-yEuyCaxSiO2+xN1-x(0.7<x<1,0<y≤0.1)的空间群为C2/c,晶体结构与CaSiO3相同;通过在La1-x-yEuyCaxSiO2+xN1-x(0≤x<1,0<y≤0.1)基质中固溶激活剂Eu获得系列蓝光、绿光、黄光荧光材料。优选地,通过引入合适含量的Ca元素,可显著降低Eu3+的含量,大幅提高量子产率。
本发明还提供所述氮氧化物荧光材料的制备方法,该制备方法合成温度低,操作方便,安全性高。
最后,本发明还保护所述氮氧化物荧光材料在照明领域的应用,及其对应的发光装置。
具体方案如下:
一种氮氧化物荧光材料,所述氮氧化物荧光材料的分子式为La1-x-yEuyCaxSiO2+ xN1-x,其中,0≤x<1,0<y≤0.1,所述氮氧化物荧光材料的基质中固溶激活剂Eu而被激活,从而具有发光特性。
进一步的,当0≤x≤0.1时,所述氮氧化物荧光材料的空间群为C2/c,晶体结构与LaSiO2N相同;
任选的,当0.1<x≤0.7时,所述氮氧化物荧光材料的空间群为P63/m,晶体结构与La5Si3O12N相同;
任选的,当0.7<x<1时,所述氮氧化物荧光材料的的空间群为C2/c,晶体结构与CaSiO3相同。
进一步的,所述氮氧化物荧光材料是由La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体、Eu2O3和/或EuF3和/或EuCl2粉体按分子式中的化学计量比混合后烧结得到。
进一步的,所述氮氧化物荧光材料在250~500nm波长入射光激发下发出波长在400~700nm范围的波长具有峰值的荧光。
进一步的,当0.8≤x<1时,所述氮氧化物荧光材料在紫外光激发下发射出蓝色荧光;
任选的,当0.2≤x<0.8时,所述氮氧化物荧光材料在紫外光激发下发射出绿色荧光;
任选的,当0≤x<0.2时,所述氮氧化物荧光材料在紫外光激发下发射出黄色荧光。
进一步的,所述氮氧化物荧光材料的结晶以包含其它结晶或非结晶化合物的混合物的方式被生成,在混合物中所述氮氧化物荧光材料结晶的质量含量不少于40%。
本发明还保护所述氮氧化物荧光材料的制备方法,包括以下步骤:
(1)混料:按照所述分子式的化学计量比分别称取La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体、Eu2O3和/或EuF3和/或EuCl2粉体作为起始原料,充分混合均匀制得原料混合物;
(2)烧结:将所得的原料混合物在氮气-氢气混合气氛或者氮气-氢气-氨气的混合气氛下、于1300~1550℃温度范围保温烧结2~6小时获得所述氮氧化物荧光材料。
进一步的,步骤(1)中,所述各粉体的粒径为微米、亚微米或纳米级;
任选的,步骤(2)中,所述混合气氛为常压或者微正压。
任选的,步骤(2)包括2a:将所得的原料混合物在氮气-氢气混合气氛或者氮气-氢气-氨气的混合气氛下、于1300~1550℃温度范围保温烧结2~6小时;2b保温烧结结束后,继续在大于1000℃且小于烧结温度的条件下、在氢气气氛中保温1~10小时进行热处理,得到所述氮氧化物荧光材料。
本发明还保护所述氮氧化物荧光材料在照明领域中的应用,所述氮氧化物荧光材料在250~500nm波长入射光激发下,发出波长在400~700nm范围的波长具有峰值的荧光。
本发明还保护一种发光装置,包括激发光源,以及所述氮氧化物荧光材料,所述激发光源为紫外激发光源。
有益效果:
本发明制备了紫外光激发的系列氮氧化物荧光材料,分子通式为La1-x- yEuyCaxSiO2+xN1-x(0≤x<1,0<y≤0.1),其中La1-x-yEuyCaxSiO2+xN1-x(0≤x≤0.1,0<y≤0.1)的空间群为C2/c,晶体结构与LaSiO2N相同;La1-x-yEuyCaxSiO2+xN1-x(0.1<x≤0.7,0<y≤0.1)的空间群为P63/m,晶体结构与La5Si3O12N相同;La1-x-yEuyCaxSiO2+xN1-x(0.7<x<1,0<y≤0.1)的空间群为C2/c,晶体结构与CaSiO3相同。
进一步地,本发明确定了LaSiO2N的晶体结构为单斜而非六方,其空间群为C2/c,La1-x-yEuyCaxSiO2+xN1-x(0≤x≤0.1,0<y≤0.1)的晶体结构与之相同,空间群也为C2/c,这对研究其稀土掺杂的光学性能十分重要。
再则,为了减低LaSiO2N:Eu荧光材料中Eu3+对发光性能的不利影响,本发明通过组成优化大量尝试,控制Ca元素在材料中的含量,当0.1<x≤0.7,发射光谱仅有Eu2+的宽带发射,具有较好的荧光性能;优选地,当x=0.5时,量子产率显著提高,从13.9%(x=0)提高到54.7%。
最后,本发明提供的La1-x-yEuyCaxSiO2+xN1-x(0≤x≤0.1,0<y≤0.1)氮氧化物荧光材料的固相烧结制备方法,合成温度低,操作简单,易于批量化生产。
附图说明
为了更清楚地说明本发明的技术方案,下面将对附图作简单的介绍,显而易见地,下面描述中的附图仅仅涉及本发明的一些实施例,而非对本发明的限制。
图1为本发明基于密度泛函理论(DFT)计算构建的LaSiO2N的晶体结构图;
图2为本发明实施例1,化学组成为LaSiO2N的样品的同步衍射及结构精修数据图;
图3为本发明实施例1,化学组成为LaSiO2N的样品的TEM及选取衍射数据图;
图4为本发明实施例1-11,化学组成分别为La0.995-xEu0.005CaxSiO2+xN1-x(x=0)(简写为La-N 100%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.1)(简写为Ca-O 10%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.2)(简写为Ca-O 20%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.3)(简写为Ca-O 30%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.4)(简写为Ca-O 40%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.5)(简写为Ca-O 50%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.6)(简写为Ca-O 60%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.7)(简写为Ca-O 70%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.8)(简写为Ca-O 80%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.9)(简写为Ca-O 90%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.995)(简写为Ca-O 100%)的系列样品的XRD衍射图谱;
图5为本发明实施例1-11,化学组成分别为La0.995-xEu0.005CaxSiO2+xN1-x(x=0)(简写为La-N 100%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.1)(简写为Ca-O 10%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.2)(简写为Ca-O 20%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.3)(简写为Ca-O 30%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.4)(简写为Ca-O 40%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.5)(简写为Ca-O 50%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.6)(简写为Ca-O 60%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.7)(简写为Ca-O 70%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.8)(简写为Ca-O 80%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.9)(简写为Ca-O 90%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.995)(简写为Ca-O 100%)的系列样品在紫外光激发下的发射光谱图;
图6为本发明实施例1-11,化学组成分别为La0.995-xEu0.005CaxSiO2+xN1-x(x=0)(简写为La-N 100%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.1)(简写为Ca-O 10%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.2)(简写为Ca-O 20%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.3)(简写为Ca-O 30%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.4)(简写为Ca-O 40%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.5)(简写为Ca-O 50%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.6)(简写为Ca-O 60%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.7)(简写为Ca-O 70%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.8)(简写为Ca-O 80%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.9)(简写为Ca-O 90%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.995)(简写为Ca-O 100%)的系列样品在紫外光激发下的量子产率图;
图7为本发明实施例6,化学组成为La0.995-xEu0.005CaxSiO2+xN1-x(x=0.5)(简写为Ca-O 50%)的样品的TEM及选取衍射数据图;
图8为本发明对比例提供的对比样品在紫外光激发下的量子产率图。
具体实施方式
下面给出本发明中使用的部分术语的定义,其他未述及的术语具有本领域所公知的定义和含义:
荧光材料:本发明中制备的荧光材料为氮氧化物,分子式为La0.995- xEu0.005CaxSiO2+xN1-x,其中,0≤x<1,所述氮氧化物荧光材料的基质中固溶激活剂Eu而被激活,从而具有发光特性。固溶激活剂Eu通过添加Eu2O3和/或EuF3和/或EuCl2粉体,与La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体混合烧结而实现。
所述氮氧化物荧光材料中,当x取值变化时,材料的晶体结构和荧光特性发生变化,这种变化使得材料可以被调控地实现多种功能,以适用于不同的运用场景。
具体的,当0≤x≤0.1时,所述氮氧化物荧光材料的空间群为C2/c,晶体结构与LaSiO2N相同;优选x=0.1,此时样品的荧光光谱中Eu3+的相对强度较低,对应Eu3+的相对强度较高;当0.1<x≤0.7时,所述氮氧化物荧光材料的空间群为P63/m,晶体结构与La5Si3O12N相同;优选x=0.4或者0.5,此时样品的量子效率较高;当0.7<x<1时,所述氮氧化物荧光材料的的空间群为C2/c,晶体结构与CaSiO3相同;优选x=1,此时样品的荧光光谱中Eu3+的相对强度较低,对应Eu3+的相对强度较高。
在荧光特性上,当0.8≤x<1时,所述氮氧化物荧光材料在紫外光激发下发射出蓝色荧光,优选x=0.9或者0.99;当0.2≤x<0.8时,所述氮氧化物荧光材料在紫外光激发下发射出绿色荧光,优选x=0.4或者0.5;当0≤x<0.2时,所述氮氧化物荧光材料在紫外光激发下发射出黄色荧光,优选x=0.1或者0.19。
本发明所述氮氧化物荧光材料的制备方法包括以下步骤:
(1)混料:按照所述分子式的化学计量比分别称取La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体、Eu2O3和/或EuF3和/或EuCl2粉体作为起始原料,充分混合均匀制得原料混合物;优选地,各粉体的粒径为微米、亚微米或纳米级;
(2)烧结:将所得的原料混合物在氮气-氢气混合气氛或者氮气-氢气-氨气的混合气氛下、于1300~1550℃温度范围保温烧结2~6小时获得所述氮氧化物荧光材料。优选地,混合气氛为常压或者微正压,例如压力为0.1-3MPa,优选为0.5-1.5MPa,更优选为0.8-1MPa。优选地,保温烧结温度1400-1500℃,更优选为1420-1480℃,例如1430℃,1450℃或者1460℃。
为了进一步提高材料中Eu2+的含量,可以在保温烧结结束后,继续在大于1000℃且小于烧结温度的条件下、在氢气气氛中保温1~10小时进行热处理,以提高材料的荧光性能。保温烧结完成后,或者热处理完成后,还可以通过粉碎、表面包覆、和分级处理中的至少一种方法对所得的材料进行粒度调整和表面修饰。
下面将更详细地描述本发明的优选实施方式。虽然以下描述了本发明的优选实施方式,然而应该理解,可以以各种形式实现本发明而不应被这里阐述的实施方式所限制。实施例中未注明具体技术或条件者,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。在下面的实施例中,如未明确说明,“%”均指重量百分比。
实施例1-11
本发明实施例1-11提供了11种Eu2+激活的La1-x-yEuyCaxSiO2+xN1-x(0≤x<1)氮氧化物荧光材料,从实施例1到实施例11,各氮氧化物荧光材料的化学式分别为:La0.995- xEu0.005CaxSiO2+xN1-x(x=0)(简写为La-N 100%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.1)(简写为Ca-O 10%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.2)(简写为Ca-O 20%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.3)(简写为Ca-O 30%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.4)(简写为Ca-O 40%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.5)(简写为Ca-O 50%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.6)(简写为Ca-O 60%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.7)(简写为Ca-O 70%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.8)(简写为Ca-O 80%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.9)(简写为Ca-O 90%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.995)(简写为Ca-O 100%)。
上述11种氮氧化物荧光材料的制备方法,包括以下步骤:
按化学计量比称取La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体、Eu2O3粉体作为起始原料,具体的原料质量见表1,之后充分混合均匀获得原料混合物,将所得的原料混合物在氮气-氢气混合气氛或者氮气-氢气-氨气混合气氛下加热到烧结温度保温烧结4小时,具体的烧结温度见表1,之后随炉冷却,从炉中取出样品,研磨,粉碎,进行后续相关测试。
表1起始原料质量和烧结温度表
图1为本发明基于密度泛函理论(DFT)计算构建的LaSiO2N的晶体结构;a为La-Si-O-N的相图;b为基于DFT构建的空间群为P6122(178)的结构模型;c为基于DFT构建的空间群为C2/c(15)的结构模型。DFT计算的结果表明:从理论角度,LaSiO2N存在两个的晶体结构模型,分别为P6122(178)和C2/c(15)。
图2示出了本发明实施例1,化学组成为LaSiO2N的样品的同步衍射及结构精修数据,结果表明,从实验层面上,LaSiO2N的空间群为C2/c(15),属单斜晶系,也即该晶系更加稳定。
图3示出了本发明实施例1,化学组成为LaSiO2N的样品的TEM及选取衍射数据,结果表明LaSiO2N的空间群为C2/c(15),属单斜晶系。
图4示出了本发明实施例1-11系列样品的XRD衍射图谱。结果表明:0≤x≤0.1的空间群为C2/c,晶体结构与LaSiO2N相同,属单斜晶系;0.1<x≤0.7的空间群为P63/m,晶体结构与La5Si3O12N相同,属六方晶系;0.7<x≤1的空间群为C2/c,属单斜晶系。
图5示出了本发明实施例1-11系列样品在紫外光激发下的发射光谱图。结果表明:0≤x≤0.1,随着Ca含量增加,Eu3+的发光强度明显降低,说明Eu3+含量降低;0.1<x≤0.7,发射光谱仅有Eu2+的宽带发射;0.7<x≤1,Eu3+的含量又增加。
图6示出了本发明实施例1-11系列样品在紫外光激发下的量子产率。结果表明:本发明所述材料可以将La0.995-xEu0.005CaxSiO2+xN1-x的效率从13.9%(x=0)提高到54.7%(x=0.5),体现了本发明的先进性。
图7示出了本发明实施例6,化学组成为La0.995-xEu0.005CaxSiO2+xN1-x(x=0.5)的样品的TEM及选取衍射数据,结果表明La0.995-xEu0.005CaxSiO2+xN1-x(x=0.5)的空间群为P63/m,属六方晶系。
对实施例1-11提供的荧光材料在紫外光激发下进行荧光检测,发射光谱峰值波长见表2。表2为中各荧光材料的化学组成分别为La0.995-xEu0.005CaxSiO2+xN1-x(x=0)(简写为La-N 100%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.1)(简写为Ca-O 10%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.2)(简写为Ca-O 20%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.3)(简写为Ca-O 30%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.4)(简写为Ca-O 40%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.5)(简写为Ca-O 50%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.6)(简写为Ca-O 60%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.7)(简写为Ca-O 70%),La0.995- xEu0.005CaxSiO2+xN1-x(x=0.8)(简写为Ca-O 80%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.9)(简写为Ca-O 90%),La0.995-xEu0.005CaxSiO2+xN1-x(x=0.995)(简写为Ca-O 100%)。
表2荧光材料的发射光谱峰值波长表
从表2可以看到,本发明实现了发射光谱可调的La1-x-yEuyCaxSiO2+xN1-x(0≤x≤0.1,0<y≤0.1)系列蓝光、绿光、黄光荧光材料。
工业应用性:
本发明确定了LaSiO2N的晶体结构为单斜而非六方,其空间群为C2/c,进一步的,为了减低LaSiO2N:Eu荧光材料中Eu3+对发光性能的不利影响,本发明通过组成优化大量尝试,获得量子产率显著提高、发射光谱可调的La1-x-yEuyCaxSiO2+xN1-x(0≤x≤0.1,0<y≤0.1)系列蓝光、绿光、黄光荧光材料。本发明的制备工艺简单,原料易得,成本低廉,极大地丰富了用于照明领域的氮氧化物荧光材料种类。可以预期,本发明的系列荧光材料及量子产率的提升方法能得到广泛地应用,极大促进荧光材料产业及其应用领域的发展。
对比例1-3
对比例1-3参照实施例2的制备方法进行,对比例1-3与实施例2所不同的是,原材料上不使用CaCO3,而是分别采用MgCO3、SrCO3、BaCO3替换CaCO3,相应的用量按照化学计量比计算,依次合成La0.995-xEu0.005MgxSiO2+xN1-x(x=0.1)、La0.995-xEu0.005SrxSiO2+xN1-x(x=0.1)、La0.995-xEu0.005BaxSiO2+xN1-x(x=0.1)三种对比样品。对比样品中按化学计量比计Mg、Sr、Ba皆为10%,与实施例2中La0.995-xEu0.005CaxSiO2+xN1-x(x=0.1)的Ca按化学计量比计为10%保持一致。
对所制备的对比样品进行量子产率分析,结果见图8,其中Mg 10%、Ca 10%、Sr10%、Ba 10%分别代表材料La0.995-xEu0.005MgxSiO2+xN1-x(x=0.1)、La0.995-xEu0.005CaxSiO2+ xN1-x(x=0.1)、La0.995-xEu0.005SrxSiO2+xN1-x(x=0.1)、La0.995-xEu0.005BaxSiO2+xN1-x(x=0.1)。
从图8可以看到,按化学计量比计算,与10%Ca取代10%La的效果相比,用同主族的Mg、Sr、Ba取代后样品的量子效率明显下降,可见从性能最优化的角度考虑,本发明的Ca取代具有明显优势和先进性。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合。为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (12)
1.一种氮氧化物荧光材料,其特征在于,所述氮氧化物荧光材料的分子式为La1-x- y Eu y Ca x SiO2+x N1-x ,其中,0.3≤x≤0.5,0<y≤0.1,所述氮氧化物荧光材料的基质中固溶激活剂Eu而被激活,从而具有发光特性。
2.根据权利要求1所述氮氧化物荧光材料,其特征在于,所述氮氧化物荧光材料的空间群为P63/m,晶体结构与La5Si3O12N相同。
3.根据权利要求1所述氮氧化物荧光材料,其特征在于,所述氮氧化物荧光材料是由La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体、Eu2O3和/或EuF3和/或EuCl2粉体按分子式中的化学计量比混合后烧结得到。
4.根据权利要求1所述氮氧化物荧光材料,其特征在于,所述氮氧化物荧光材料在250~500nm波长入射光激发下发出波长在400~700nm范围的波长具有峰值的荧光。
5.根据权利要求4所述氮氧化物荧光材料,其特征在于,所述氮氧化物荧光材料在紫外光激发下发射出绿色荧光。
6.根据权利要求1-5中任一项所述氮氧化物荧光材料,其特征在于,所述氮氧化物荧光材料的结晶以包含其它结晶或非结晶化合物的混合物的方式被生成,在混合物中所述氮氧化物荧光材料结晶的质量含量不少于40%。
7.一种权利要求1-6中任一项所述氮氧化物荧光材料的制备方法,其特征在于,包括以下步骤:
(1)混料:按照所述分子式的化学计量比分别称取La2O3粉体、CaCO3粉体、Si3N4粉体、SiO2粉体、Eu2O3和/或EuF3和/或EuCl2粉体作为起始原料,充分混合均匀制得原料混合物;
(2)烧结:将所得的原料混合物在氮气-氢气混合气氛或者氮气-氢气-氨气的混合气氛下、于1300~1550℃温度范围保温烧结2~6小时获得所述氮氧化物荧光材料。
8.根据权利要求7所述氮氧化物荧光材料的制备方法,其特征在于,步骤(1)中,所述各粉体的粒径为微米、亚微米或纳米级。
9.根据权利要求7所述氮氧化物荧光材料的制备方法,其特征在于,步骤(2)中,所述混合气氛为常压或者微正压。
10.根据权利要求7所述氮氧化物荧光材料的制备方法,其特征在于,步骤(2)包括2a:将所得的原料混合物在氮气-氢气混合气氛或者氮气-氢气-氨气的混合气氛下、于1300~1550℃温度范围保温烧结2~6小时;2b保温烧结结束后,继续在大于1000℃且小于烧结温度的条件下、在氢气气氛中保温1~10小时进行热处理,得到所述氮氧化物荧光材料。
11.一种权利要求1-6中任一项所述氮氧化物荧光材料在照明领域中的应用,其特征在于,所述氮氧化物荧光材料在250~500nm波长入射光激发下,发出波长在400~700nm范围的波长具有峰值的荧光。
12.一种发光装置,包括激发光源,以及权利要求1-6任一项所述氮氧化物荧光材料,其特征在于:所述激发光源为紫外激发光源。
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