CN106398688A - 一种应用于新生儿黄疸病治疗led器件中的蓝光荧光粉及其合成方法 - Google Patents
一种应用于新生儿黄疸病治疗led器件中的蓝光荧光粉及其合成方法 Download PDFInfo
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Abstract
一种应用于新生儿黄疸病治疗LED器件中的蓝光荧光粉及其合成方法,其化学组成式为:SiO2‑Mg1‑xCl2:Eu2+ x;其中0.001≤x≤0.90。上述蓝色荧光粉的合成方法,包括如下步骤:将MgO、SiO2和Eu2O3在500~1000℃,空气气氛中煅烧1~5h,形成荧光粉A;再次将荧光粉A研磨后,将荧光粉A在500~1000℃的还原气氛中煅烧1~5h,形成最终的蓝光荧光粉。所述反应是在陶瓷坩埚和管式还原炉中进行。(1)本发明所得的荧光粉为石英型结构,所用原料无毒、价廉易得;合成方法采用高温固相反应,具有合成方法简单,合成时间短等优点。(2)本发明产品所含紫外线含量占整体荧光发射量的千分之一不到,且较完美地覆盖了光照治疗黄疸病所需的辐射范围,提高了能量利用率与安全性。
Description
技术领域
本发明属于无机材料的稀土掺杂荧光粉,具体地说,涉及一种应用于新生儿黄疸病治疗LED器件中的蓝光荧光粉及其合成方法。
背景技术
光照治疗是新生儿黄疸病治疗中的一种方法。由于光照治疗不像药物治疗对新生儿产生毒性,也不像换血疗法一样对新生儿产生过重的身体负担,所以它是新生儿黄疸病治疗中最常用的方法。光照疗法中使用蓝光,作为蓝光光源,最常用的为蓝色荧光粉与激发芯片组合而成的LED器件。所以蓝光荧光粉的开发有着广阔的应用前景。
患黄疸病的新生儿皮肤首先吸收蓝光,然后蓝光将皮肤中的胆红素氧化掉,使之产生一种极性较强、可随尿液排出的氧化物而从身体中代谢出去。400-520nm范围内的蓝光对此治疗都有效,特别是460±10nm的蓝光与胆红素的吸收光谱更加匹配。目前用于此光照治疗的蓝光荧光粉都存在既发射蓝光,也发射一定紫外光的问题。首先,这浪费了一定的能量,不环保。其次,紫外线辐射对于新生儿的伤害较大,不利于健康。所以开发新型紫外线含量低的、高效的蓝光荧光粉是目前急需解决的问题。
发明内容
本发明的目的在于克服现有技术的缺点,提供一种紫外线含量低,用于新生儿黄疸病治疗LED器件中的蓝光荧光粉及其合成方法。
为了实现上述目的,本发明采用如下技术方案:
一种蓝光荧光粉,其化学组成式为:SiO2-Mg1-xCl2:Eu2+ x;其中0.001≤x≤0.90。
上述蓝色荧光粉的合成方法,包括如下步骤:将MgO、SiO2和Eu2O3在500~1000℃,空气气氛中煅烧1~5h,形成荧光粉A;再次将荧光粉A研磨后,将荧光粉A在500~1000℃的还原气氛中煅烧1~5h,形成最终的蓝光荧光粉。所述反应是在陶瓷坩埚和管式还原炉中进行。
与现有的荧光粉相比,本发明具有如下有益效果:
(1)本发明所得的荧光粉为α-石英型结构,所用原料无毒、价廉易得;合成方法采用高温固相反应,具有合成方法简单,合成时间短等优点。
(2)本发明产品所含紫外线含量占整体荧光发射量的千分之一不到,且较完美地覆盖了光照治疗黄疸病所需的辐射范围,提高了能量利用率与安全性。
附图说明
图1为本发明实验例1~3所制备的蓝色荧光粉的XRD图。
图2为本发明实施例1所制备的蓝色荧光粉的荧光激发光谱图。
图3为本发明实施例1所制备的蓝色荧光粉的荧光发射光谱图。
图4为本发明实施例1所制备的蓝色荧光粉的荧光发射变温光谱图。其中,图4中,是荧光粉的升温曲线,曲线从上到下,温度升高,荧光强度降低。
图5为本发明实施例1所制备的蓝色荧光粉的漫反射谱图。
具体实施方式
为更好理解本发明,下面结合实施例对本发明做进一步地详细说明,但是本发明要求保护的范围并不局限于实例表示的范围。
实施例1:蓝色荧光粉的制备
将0.01mol的MgO、0.02mol的NH4Cl、0.03mol的SiO2和1.2×10—4mol(0.3mol%)的Eu2O3放入玛瑙研钵中研磨1小时至混合均匀。放入陶瓷坩埚中,然后在高温炉中,加热至1000℃,保温2小时,然后自然冷却。取出样品后放入玛瑙研钵,再加入0.02mol的NH4Cl,研磨至充分混匀。然后放入陶瓷坩埚中,装入管式还原炉中,在H2:N2体积比例为1:9的还原气氛中,加热至1000℃,保温2小时,然后自然冷却,取出后研磨再进行后续测试。产品的XRD衍射峰如图1所示;荧光激发光谱如图2所示;荧光发射光谱如图3所示;荧光发射变温光谱图如图4;蓝色荧光粉的漫反射谱图如图5。如图1中谱线1所示,所有衍射峰都能与底部的α-石英型结构的标准峰(JCPDS No.46-1045)相对应,由此可知所得产物为纯的α-石英型结构。将此荧光粉紫外光部分与整体荧光发射部分分别作积分,然后相除得到紫外光部分占整个荧光发射部分的比例,该比例不足0.1%,证明本荧光粉紫外辐射极少,安全性高。
实施例2:蓝色荧光粉的制备
将0.01mol的MgO、0.02mol的NH4Cl、0.03mol的SiO2和2.4×10—4mol(0.6mol%)的Eu2O3放入玛瑙研钵中研磨1小时至混合均匀。放入陶瓷坩埚中,然后在高温炉中,加热至1000℃,保温2小时,然后自然冷却。取出样品后放入玛瑙研钵,再加入0.02mol的NH4Cl,研磨至充分混匀。然后放入陶瓷坩埚中,装入管式还原炉中,在H2:N2体积比例为1:9的还原气氛中,加热至1000℃,保温2小时,然后自然冷却,取出后研磨再进行后续测试。产品的XRD衍射峰如图1所示。如图1中谱线2所示,所有衍射峰都能与底部的α-石英型结构的标准峰(JCPDS No.46-1045)相对应,由此可知所得产物为纯的α-石英型结构。实施例2的荧光激发光谱图,荧光发射光谱图,荧光发射变温光谱图,蓝色荧光粉的漫反射谱图均与实施例1一致。
实施例3:蓝色荧光粉的制备
将0.01mol的MgO、0.02mol的NH4Cl、0.03mol的SiO2和1.2×10—4mol(0.3mol%)的Eu2O3放入玛瑙研钵中研磨1小时至混合均匀。放入陶瓷坩埚中,然后在高温炉中,加热至900℃,保温2小时,然后自然冷却。取出样品后放入玛瑙研钵,再加入0.02mol的NH4Cl,研磨至充分混匀。然后放入陶瓷坩埚中,装入管式还原炉中,在H2:N2体积比例为2:8的还原气氛中,加热至900℃,保温1.5小时,然后自然冷却,取出后研磨再进行后续测试。产品的XRD衍射峰如图1所示。如图1中谱线3所示,所有衍射峰都能与底部的α-石英型结构的标准峰(JCPDSNo.46-1045)相对应,由此可知所得产物为纯的α-石英型结构。实施例3的荧光激发光谱图,荧光发射光谱图,荧光发射变温光谱图,蓝色荧光粉的漫反射谱图均与实施例1一致。
Claims (3)
1.一种蓝光荧光粉,其化学组成式为:SiO2-Mg1-xCl2:Eu2+ x;其中0.001≤x≤0.90。
2.权利要求1所述蓝色荧光粉的合成方法,其特征在于包括如下步骤:将MgO、SiO2和Eu2O3在500~1000℃,空气气氛中煅烧1~5h,形成荧光粉A;再次将荧光粉A研磨后,将荧光粉A在500~1000℃的还原气氛中煅烧1~5h,形成最终的蓝光荧光粉。
3.如权利要求1所述的蓝色荧光粉的合成方法,其特征在于,所述反应是在陶瓷坩埚和管式还原炉中进行。
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CN112971708A (zh) * | 2019-12-12 | 2021-06-18 | 上海交通大学 | 基于皮肤荧光谱分析的胆红素无创检测装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1640985A (zh) * | 2004-01-06 | 2005-07-20 | 孙家跃 | 365nm紫外线激活的颜色可调蓝色荧光材料 |
CN1677695A (zh) * | 2004-03-29 | 2005-10-05 | 宏齐科技股份有限公司 | 白光发光二极管单元 |
US20060279196A1 (en) * | 2005-06-02 | 2006-12-14 | Wei-Jen Hsu | White LED |
CN101517035A (zh) * | 2006-09-27 | 2009-08-26 | 奥斯兰姆奥普托半导体有限责任公司 | 发射辐射装置 |
CN102226086A (zh) * | 2011-04-23 | 2011-10-26 | 龙南县顺德明辉荧光材料有限责任公司 | 一种稀土卤硅酸盐红色长余辉荧光粉及其制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1640985A (zh) * | 2004-01-06 | 2005-07-20 | 孙家跃 | 365nm紫外线激活的颜色可调蓝色荧光材料 |
CN1677695A (zh) * | 2004-03-29 | 2005-10-05 | 宏齐科技股份有限公司 | 白光发光二极管单元 |
US20060279196A1 (en) * | 2005-06-02 | 2006-12-14 | Wei-Jen Hsu | White LED |
CN101517035A (zh) * | 2006-09-27 | 2009-08-26 | 奥斯兰姆奥普托半导体有限责任公司 | 发射辐射装置 |
CN102226086A (zh) * | 2011-04-23 | 2011-10-26 | 龙南县顺德明辉荧光材料有限责任公司 | 一种稀土卤硅酸盐红色长余辉荧光粉及其制备方法 |
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CN112971708A (zh) * | 2019-12-12 | 2021-06-18 | 上海交通大学 | 基于皮肤荧光谱分析的胆红素无创检测装置 |
CN112971708B (zh) * | 2019-12-12 | 2022-07-15 | 上海交通大学 | 基于皮肤荧光谱分析的胆红素无创检测装置 |
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