CN111117605B - 一种有机铝纳米晶及其制备方法和应用 - Google Patents
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Abstract
本发明涉及发光和照明技术领域,具体涉及一种有机铝纳米晶及其制备方法和应用。本发明提供的有机铝纳米晶为乙酰丙酮铝纳米晶,所述乙酰丙酮铝纳米晶的空间群为单斜晶系P21/c,平均粒径为1.4‑5.5nm。本发明还提供了制备方法,包括:(1)将有机铝盐在惰性气氛下150‑200℃加热处理,得到有机铝盐前驱体;(2)将所述有机铝盐前驱体溶于有机溶剂中,然后置于超声粉碎机中超声粉碎,得到有机铝纳米晶。本发明所得到的有机铝纳米晶的发光强度高,稳定性好,由其制备得到的UV型远程白光LED器件,显色指数高达91,为设计新的照明和显示器件结构开辟了道路。
Description
技术领域
本发明涉及发光和照明技术领域,具体涉及一种有机铝纳米晶及其制备方法和应用。
背景技术
荧光转换型白光LED(pc-WLEDs)已经在照明和显示等领域得到广泛应用,其主流技术为蓝光芯片激发荧光粉策略。但是,该器件结构还面临着亟待解决的问题:(i)蓝光芯片工作的温度可达到100-150℃,荧光粉存在热降解;(ii)采用不同颜色荧光粉直接混合策略可以得到高品质的pc-WLEDs器件,但是荧光粉之间存在重吸收;(iii)由蓝光芯片发射的450-500nm的强蓝光会引起视网膜损伤。
针对上述问题,采用紫外激发的远程白光LED不仅能降低荧光粉的热降解和重吸收,还能延缓蓝光芯片导致的蓝光损害。蓝光发光材料是制备UV型远程白光LED的核心材料。近年来,纳米发光材料领域发展迅速,提供了多种发光纳米晶材料,例如:硒化镉、磷化铟、钙钛矿、碳点等纳米材料,然而这些纳米材料的光热稳定性比较差,限制了其在UV型LED中的应用。因此发展新型蓝光纳米晶材料亦是UV型远程白光LED技术领域研究方向之一。
此外,UV型远程白光LED技术通过增大荧光粉和芯片的距离以减小对荧光粉的热损耗的策略,使其需要开发荧光转换薄膜。
发明内容
针对现有的荧光转换型白光LED器件升级需求,本发明的目的之一在于提供一种蓝光有机铝纳米晶,所述有机铝纳米晶为乙酰丙酮铝纳米晶,其平均粒径为1.4-5.5nm,多发射峰,荧光量子产率可达90%以上,发光性能和稳定性能好。
本发明的目的之二在于提供一种蓝光有机铝纳米晶的制备方法,其操作简单,成本低,适合大规模工业化生产应用。
本发明的目的之三在于提供一种蓝光复合薄膜,其由上述有机铝纳米晶或上述制备方法制备得到的有机铝纳米晶与聚合物树脂构成。本发明提供的蓝光复合薄膜利用蓝光有机铝纳米晶与聚合物树脂之间极好的兼容性,制备高质量的蓝光有机铝纳米晶/聚合物复合薄膜。该薄膜具有高的量子产率和极高的透过率,适合用作紫外激发型远程白光LED器件中的蓝光薄膜发光材料。
本发明的目的之四在于提供一种UV型远程白光LED器件,包括紫外芯片和光转化层,所述光转化层通过上述蓝光复合薄膜、红光CuInS2复合薄膜和绿光CuInS2复合薄膜制备得到。
具体来说,本发明提供了如下技术方案。
一种有机铝纳米晶,所述有机铝纳米晶为乙酰丙酮铝纳米晶,所述乙酰丙酮铝纳米晶的空间群为单斜晶系P21/c,平均粒径为1.4-5.5nm。
优选的,上述有机铝纳米晶中,所述乙酰丙酮铝纳米晶的激发波长为350-400nm,发射波长为400-470nm,最大激发波长为375nm。
优选的,上述有机铝纳米晶中,所述乙酰丙酮铝纳米晶的荧光量子产率大于80%,优选为大于90%。
本发明还提供一种有机铝纳米晶的制备方法,其包括以下步骤:
(1)将有机铝盐在惰性气氛下150-200℃加热处理,得到有机铝盐前驱体;
(2)将所述有机铝盐前驱体溶于有机溶剂中,然后置于超声粉碎机中超声粉碎,得到有机铝纳米晶。
优选的,上述制备方法中,步骤(1)中,所述有机铝盐为乙酰丙酮铝。
优选的,上述制备方法中,步骤(1)中,所述加热处理的时间为0.5-2h,优选为1.5-2h。
优选的,上述制备方法中,步骤(2)中,所述有机溶液为甲苯、正己烷、环己烷、对二甲苯或氯仿。
优选的,上述制备方法中,步骤(2)中,所述超声粉碎的功率为75-100W,优选的,所述超声粉碎的时间为4-8h。
本发明还提供一种复合薄膜,由上述的有机铝纳米晶或上述制备方法制备得到的有机铝纳米晶与聚合物树脂构成。
本发明还提供一种白光LED器件,其包括紫外芯片和光转化层,所述光转化层通过上述的复合薄膜、红光CuInS2复合薄膜和绿光CuInS2复合薄膜制备得到
本发明所取得的有益效果:
1、本发明的有机铝纳米晶的荧光量子产率可达90%以上,发光强度高,稳定性好,低毒,含量丰富,制备工艺简单;
2、本发明的有机铝纳米晶与聚合物树脂有极好的兼容性,由其制备的有机铝纳米晶/聚合物复合薄膜的荧光量子产率可达40-60%,透过率可超过80-90%;
3、本发明将制备的蓝光有机铝纳米晶/聚合物复合薄膜与红光CuInS2复合薄膜、绿光CuInS2复合薄膜共同作为三基色光转换层用于制备UV型远程白光LED器件,其显色指数高达91,与传统的蓝光芯片激发荧光粉制备白光LED相比,不仅能够有效避免荧光粉的热降解和重吸收,还能降低蓝光芯片导致的蓝光损害问题。这为设计新的照明和显示器件结构开辟了道路。
附图说明
图1为实施例1-4所制备的蓝光有机铝纳米晶粉末的X射线衍射图。
图2为实施例1-4所制备的蓝光有机铝纳米晶的荧光发射光谱。
图3为实施例5所制备的纳米晶/聚甲基丙烯酸甲酯复合薄膜的在可见光区的透过率光谱图。
图4为实施例5所制备的纳米晶/聚甲基丙烯酸甲酯复合薄膜的荧光发射光谱。
图5为实施例6所制备紫外激发的远程蓝光LED的发光光谱图。
图6为实施例7所制备紫外激发的远程白光LED的器件结构图。
图7为实施例7所制备紫外激发的远程白光LED的色坐标图。
图8为对比例1制备的样品的荧光发射光谱。
图9为对比例1制备的样品的透射电镜和傅里叶衍射斑。
具体实施方式
以下结合具体实施例对本发明作进一步详细说明,但不用来限制本发明的范围。
实施例1
采用如下方法制备得到蓝光有机铝纳米晶:
a)用去离子水清洗石英舟,再置于烘干箱中烘干备用;
b)称取1.625g烘干处理过的乙酰丙酮铝,放入石英舟中;
c)将上述石英舟置于石英管中部后,置于管式炉中。调整石英管的位置,使加热温区和石英舟的位置一致。确定气密性良好后,以30sccm的速率通入30min惰性气体来排尽管内空气。将温度设置为经10min由30℃升至200℃,同时将气流速率改为10sccm,保温0.5h。最后,自然降温至室温,关闭气体,收集固体;
d)取出管式炉中的石英舟,取一定物质的量的固体溶于甲苯中。再放入超声清洗机中,设置超声功率为100W,超声时间为6h;
e)取出超声清洗机中的玻璃试剂瓶,即得到蓝光有机铝纳米晶/甲苯溶液。
f)将上述蓝光有机铝纳米晶/甲苯溶液采用真空干燥箱(60℃,-0.1MPa)烘干2h得到蓝光有机铝纳米晶粉末。
实施例2
采用如下方法制备得到蓝光有机铝纳米晶:
a)用去离子水清洗石英舟,再用置于烘干箱中烘干。
b)称取1.625g烘干处理过的乙酰丙酮铝,放入石英舟中。
c)将上述石英舟置于石英管中部后,置于管式炉中。调整石英管的位置,使加热温区和石英舟的位置一致。确定气密性良好后,以30sccm的速率通入30min惰性气体来排尽管内空气后。将温度设置为经10min由30℃升至200℃,同时将气流速率改为10sccm,保温1h。最后,自然降温至室温,关闭气体,收集固体。
d)取出管式炉中的石英舟,取一定物质的量的固体溶于甲苯中。再放入超声清洗机中,设置超声功率为100W,超声时间为6h。
e)取出超声清洗机中的玻璃试剂瓶,即得到蓝光有机铝纳米晶/甲苯溶液。
f)将上述蓝光有机铝纳米晶/甲苯溶液采用真空干燥箱(60℃,-0.1MPa)烘干2h得到蓝光有机铝纳米晶粉末。
实施例3
采用如下方法制备得到蓝光有机铝纳米晶:
a)用去离子水清洗石英舟,再用置于烘干箱中烘干。
b)称取1.625g烘干处理过的乙酰丙酮铝,放入石英舟中。
c)将上述石英舟置于石英管中部后,置于管式炉中。调整石英管的位置,使加热温区和石英舟的位置一致。确定气密性良好后,以30sccm的速率通入30min惰性气体来排尽管内空气。将温度设置为经10min由30℃升至200℃,同时将气流速率改为10sccm,保温1.5h。最后,自然降温至室温,关闭气体,收集固体。
d)取出管式炉中的石英舟,取一定物质的量的固体溶于甲苯中。再放入超声清洗机中,设置超声功率为100W,超声时间为6h。
e)取出超声清洗机中的玻璃试剂瓶,即得到蓝光有机铝纳米晶/甲苯溶液。
f)将上述蓝光有机铝纳米晶/甲苯溶液采用真空干燥箱(60℃,-0.1MPa)烘干2h得到蓝光有机铝纳米晶粉末。
实施例4
采用如下方法制备得到蓝光有机铝纳米晶:
a)用去离子水清洗石英舟,再用置于烘干箱中烘干。
b)称取1.625g烘干处理过的乙酰丙酮铝,放入石英舟中。
c)将上述石英舟置于石英管中部后,置于管式炉中。调整石英管的位置,使加热温区和石英舟的位置一致。确定气密性良好后,以30sccm的速率通入30min惰性气体来排尽管内空气。将温度设置为经10min由30℃升至200℃,同时将气流速率改为10sccm,保温2h。最后,自然降温至室温,关闭气体,收集固体。
d)取出管式炉中的石英舟,取一定物质的量的固体溶于甲苯中。再放入超声清洗机中,设置超声功率为100W,超声时间为6h。
e)取出超声清洗机中的玻璃试剂瓶,即得到蓝光有机铝纳米晶/甲苯溶液。
f)将上述蓝光有机铝纳米晶/甲苯溶液采用真空干燥箱(60℃,-0.1MPa)烘干2h得到蓝光有机铝纳米晶粉末。
实施例1-4制备的蓝光有机铝纳米晶、原料乙酰丙酮铝和乙酰丙酮铝标准卡片的X射线衍射图(XRD)如图1所示,从图可以看出,在不同加热时间下得到的有机铝纳米晶XRD图谱的峰位和强度与原料乙酰丙酮铝一致,并与标准卡片匹配,证明所得到的有机铝纳米晶物相为单斜晶系P21/c乙酰丙酮铝。
实施例1-4制备的蓝光有机铝纳米晶的荧光发射光谱图如图2所示,从图中可以看出,在不同加热时间下得到的有机铝纳米晶呈多峰荧光特性,其峰值分别位于409nm、435nm和460nm处。
使用滨松绝对荧光量子产率测试系统,采用375nm的激发波长,测定实施例1-4得到的蓝光有机铝纳米晶的荧光量子产率分别为80.5%、81.8%、91.5%、90.7%。
使用DigitalMicrograph软件中的测量功能分别统计实施例1-4制备的蓝光有机铝纳米晶中100个纳米晶的粒径大小,并对数据做统计分析得到实施例1-4有机铝纳米晶的粒径分布分别为3.9±1.6nm、3.6±1.5nm、3.2±1.8nm和3.7±1.2nm。
实施例5
采用如下方法制备得到蓝光有机铝纳米晶/聚甲基丙烯酸甲酯复合薄膜:
a)称取1g聚甲基丙烯酸甲酯(PMMA),溶于2ml的甲苯溶液中,过夜搅拌至完全溶解且没有气泡,得到聚合物溶液;
b)将0.5ml实施例3制作的蓝光有机铝纳米晶/甲苯溶液置于步骤a)中的聚合物溶液,搅拌2h至蓝光有机铝纳米晶在聚合物溶液中均匀分散;
c)将上述含有蓝光有机铝纳米晶的聚合物溶液滴在干净的玻璃片上,用刮膜器刮平,置于通风厨中自然晾干,即可得到蓝光有机铝纳米晶/聚甲基丙烯酸甲酯复合薄膜。
实施例5制备的蓝光有机铝纳米晶/聚甲基丙烯酸甲酯复合薄膜的荧光发射光谱图如图4所示,从图中可以看出,有机铝纳米晶复合薄膜呈多峰荧光特性,其峰值分别位于405nm、434nm和461nm处。且与蓝光有机铝纳米晶溶液的荧光发射峰基本一致,说明纳米晶成功嵌入到聚合物中。
实施例5制备的蓝光有机铝纳米晶/聚甲基丙烯酸甲酯复合薄膜的透过率光谱图如图3所示,从图中可以看出,复合薄膜的透过率超过88%,在大于420nm的波长范围,透过率超过了90%。
使用滨松绝对荧光量子产率测试系统,采用355nm、375nm和395nm的激发波长,测定实施例5制备的蓝光有机铝纳米晶/聚甲基丙烯酸甲酯复合薄膜的荧光量子产率分别为40.5%、55.6%、60.3%。
实施例6
采用如下方法制备得到LED器件:
a)取实施例5制备的蓝光有机铝纳米晶/聚甲基丙烯酸甲酯复合薄膜,按照芯片支架的尺寸裁剪同样大小的蓝光复合薄膜;
b)将上述蓝光复合薄膜置于紫外LED芯片(370nm)支架上,薄膜与芯片支架之间用硅胶粘合,支架两端设有正负极引脚。
对制备得到的LED器件进行检测,测试步骤如下:依次打开高精度快速光谱辐射计电源、精密数显直流稳流稳压电源和LEDspec测试软件,选择常规测量模式,将所述LED器件放在积分球入口处,LED的正负极引脚与精密数显直流稳流稳压电源连接,对LED施加规定的正向电流IF为20mA,光度探测系统测量出光通量。在软件上显示出白光光谱以及CIE1931色品坐标、显色指数、色温、效率参数,导出数据以及光谱进行分析。
软件分析得到CIE色品坐标为(0.1750,0.1162),显色指数为43.0,流明效率为1.26lm/W,证明LED发出的光处于蓝光区域。
图5为实施例6所制备紫外激发的蓝光LED的发光光谱图。
实施例7
采用如下方法制备得到LED器件:
a)取实施例5制备的蓝光有机铝纳米晶/聚甲基丙烯酸甲酯复合薄膜、红光CuInS2复合薄膜和绿光CuInS2复合薄膜,按照芯片支架的尺寸裁剪同样大小的红光、绿光、蓝光复合薄膜;
b)如图6所示,将上述红光、绿光、蓝光复合薄膜置于紫外LED芯片(370nm)支架上,底层为红光薄膜,中间为绿色薄膜,顶层为蓝色薄膜,薄膜之间及薄膜与芯片支架之间用硅胶粘合,支架两端设有正负极引脚。
对制备得到的LED器件进行检测,测试步骤如下:依次打开高精度快速光谱辐射计电源、精密数显直流稳流稳压电源和LEDspec测试软件,选择常规测量模式;将所述LED放在积分球入口处,LED的正负极引脚与精密数显直流稳流稳压电源连接,对LED施加规定的正向电流IF、为20mA,光度探测系统测量出光通量。在软件上显示出白光光谱以及CIE 1931色品坐标、显色指数、色温、效率参数,导出数据以及光谱进行分析,图7为本实施例制备的LED器件的色坐标图。
软件分析得到CIE色品坐标为(0.462,0.396),显色指数为91,色温为2553K,证明LED发出的光处于暖白光区域。
对比例1
对比例1与实施例1的区别仅在于:对比例1步骤c)中温度设置为经10min由30℃升至330℃。
将对比例1步骤c)焙烧收集到的固体溶于甲苯中,溶液呈淡黄色且在紫外灯下呈蓝紫色。
将对比例1步骤f)得到的样品与实施例1制备的蓝光有机铝纳米晶在同样的条件下(激发波长为360nm)测试荧光发射光谱,测试结果如图8所示,可以看出对比例1得到的样品的发光峰位在395nm,而实施例1的发光峰位在409、435、460nm。进一步的,图9为对比例1得到的样品的透射电镜和傅里叶衍射斑,由图可知,该样品为多晶化合物。因此,对比例1无法制备得到乙酰丙酮铝纳米晶。
虽然,上文中已经用一般性说明、具体实施方式及试验,对本发明作了详尽的描述,但在本发明基础上,可以对其作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (10)
1.一种有机铝纳米晶的制备方法,其特征在于,包括以下步骤:
(1)将有机铝盐在惰性气氛下150-200 oC加热处理,得到有机铝盐前驱体;
(2)将所述有机铝盐前驱体溶于有机溶剂中,然后置于超声粉碎机中超声粉碎,得到有机铝纳米晶;
所述有机铝纳米晶为乙酰丙酮铝纳米晶,所述乙酰丙酮铝纳米晶的空间群为单斜晶系P21/c,平均粒径为1.4-5.5nm。
2.根据权利要求1所述的制备方法,其中,步骤(1)中,所述有机铝盐为乙酰丙酮铝。
3.根据权利要求1或2所述的制备方法,其中,步骤(1)中,所述加热处理的时间为0.5-2h。
4.根据权利要求3所述的制备方法,其中,步骤(1)中,所述加热处理的时间为1.5-2h。
5.根据权利要求1或2所述的制备方法,其中,步骤(2)中,所述有机溶液为甲苯、正己烷、环己烷、对二甲苯或氯仿。
6.根据权利要求3所述的制备方法,其中,步骤(2)中,所述有机溶液为甲苯、正己烷、环己烷、对二甲苯或氯仿。
7.根据权利要求1或2所述的制备方法,其中,步骤(2)中,所述超声粉碎的功率为75-100W。
8.根据权利要求7所述的制备方法,其中,步骤(2)中,所述超声粉碎的时间为4-8h。
9.根据权利要求3所述的制备方法,其中,步骤(2)中,所述超声粉碎的功率为75-100W。
10.根据权利要求5所述的制备方法,其中,步骤(2)中,所述超声粉碎的功率为75-100W。
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