CN104789212B - 一种led用白光荧光粉及其制备方法 - Google Patents
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- 239000000843 powder Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 2
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- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- MRZXYVKMVSEFLY-UHFFFAOYSA-N 4-(4-carboxy-2-methoxyphenyl)-3-methoxybenzoic acid Chemical compound COC1=CC(C(O)=O)=CC=C1C1=CC=C(C(O)=O)C=C1OC MRZXYVKMVSEFLY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及LED领域，特别涉及一种LED用白光荧光粉及其制备方法。一种LED用白光荧光粉，该荧光粉的化学分子式为C44H34N4O12MnEu。本发明的白光荧光粉合成方法简单，并且得到的白光荧光粉结构稳定；本发明的白光荧光粉采用简单的溶剂热合成法，和现有的白光荧光粉的制备方法相比，此方法无需高温焙烧，产率高，重复性好；当本发明的白光荧光粉被350nm波长的光激发时，可以发射430nm、500nm、580nm、620nm波段的光，这四个谱带叠加从而在单一基质中实现了白光发射。
Description
技术领域
本发明涉及LED领域，特别涉及一种LED用白光荧光粉及其制备方法。
背景技术
发光二极管（LED，Light
Emitting Diode）是一种新型的发光器件，它不仅具有耗电量少、寿命长、工作电压低、环保、安全、响应快、可靠性高、维护少、体积小、重量轻等优点，而且能够发出蓝光、绿光、紫光或深紫外光，使LED产生白光成为现实，是我国发展的高新技术方向。但是目前的白光多是由黄色荧光粉与LED的蓝光混合而成，具有色彩还原性差，显色指数低等问题。全色单基质白光荧光粉能在一定程度上克服上述问题，因此开发适合紫外激发的高效单基质白光荧光粉将是新一代白光LED照明的研究热点，具有广阔的经济应用价值。
发明内容
本发明所要解决的技术问题是提供一种LED用高效单基质白光荧光粉。
本发明的另一个目的在于提供上述白光荧光粉的制备方法。
一种LED用白光荧光粉，该荧光粉的化学分子式为C44H34N4O12MnEu。
进一步的，所述荧光粉为三斜晶系，P-1空间群，晶胞参数为a=21.329(2) Å，b=18.527(2) Å，c=23.048(3) Å，α=105.38(3) º，β=101.17(7) º，γ=106.39(2) º，V=9107.7
(1) Å3。
上述LED用白光荧光粉的制备方法为：将有机化合物1,4-二(咪唑-1-基)苯（1,4-Bis(imidazol-1-yl)benzene）、2,2'-二甲氧基-4,4'-联苯基二羧酸（2,2'-dimethoxy-4,4'-biphenyldicarboxylic acid）、硝酸锰、硝酸铕加入至乙腈、二甲基甲酰胺和水的混合溶剂当中，在室温下搅拌形成混合液A，然后将混合液A在75℃下回流6小时得到混合液B，再将混合液B在溶剂热条件下加热反应后缓慢降温得到所述白光荧光粉。
进一步的，所述溶剂热的加热反应温度为160℃~180℃。
进一步的，所述溶剂热的加热反应时间为24~48小时。
进一步的，所述溶剂热反应后的降温为2℃/小时~5℃/小时降至室温。
进一步的，所述1,4-二(咪唑-1-基)苯、2,2'-二甲氧基-4,4'-联苯基二羧酸、硝酸锰、硝酸铕的摩尔比为1:2:1:1。
进一步的，所述乙腈、二甲基甲酰胺和水的体积比选为1:2:2。
本发明具有如下有益效果：
本发明的白光荧光粉合成方法简单，并且得到的白光荧光粉结构稳定；本发明的白光荧光粉采用简单的溶剂热合成法，和现有的白光荧光粉的制备方法相比，此方法无需高温焙烧，产率高，重复性好；当本发明的白光荧光粉被350nm波长的光激发时，可以发射430nm、500nm、580nm、620nm波段的光，这四个谱带叠加从而在单一基质中实现了白光发射。
附图说明
图1为本发明的实施例1的荧光光谱图。
具体实施方式
下面结合实施例对本发明进行详细的说明，实施例仅是本发明的优选实施方式，不是对本发明的限定。
实施例
1
将0.1 mmol1,4-二(咪唑-1-基)苯、0.2 mmol2,2'-二甲氧基-4,4'-联苯基二羧酸、0.1 mmol硝酸锰和0.1 mmol硝酸铕溶于3mL乙腈、6mL二甲基甲酰胺和6mL水的混合溶剂当中，在室温下搅拌形成混合液A，然后将上述混合液A在75℃下回流6小时得到混合液B，再将所述混合液B置入25 mL水热反应釜中在溶剂热160℃条件下加热反应48小时后以5℃/小时降至室温得到所述的白光荧光粉。
然后将上述化合物进行结构表征。
然后将荧光粉进行结构表征。
该荧光粉的X射线衍射数据是在Bruker Smart Apex CCD面探衍射仪上，用MoKα辐射(λ =
0.71073 Å)，以ω扫描方式收集并进行Lp因子校正，吸收校正使用SADABS程序。用直接法解结构，然后用差值傅立叶法求出全部非氢原子坐标，并用理论加氢法得到氢原子位置(C−H 1.083 Å)，用最小二乘法对结构进行修正。计算工作在PC机上用SHELXTL程序包完成。
经测试解析可知，该荧光粉的化学分子式为C44H34N4O12MnEu，三斜晶系，P-1空间群，晶胞参数为a=21.329(2) Å，b=18.527(2) Å，c=23.048(3) Å，α=105.38(3) º，β=101.17(7) º，γ=106.39(2) º，V=9107.7
(1) Å3，Z=8。该荧光粉的荧光光谱图如图1所示，当激发波长为350nm时，从图中可以看出430nm、500nm、580nm、620nm波段的光，这四个谱带叠加从而在单一基质中实现了白光发射。
实施例
2
将0.1 mmol1,4-二(咪唑-1-基)苯、0.2 mmol2,2'-二甲氧基-4,4'-联苯基二羧酸、0.1 mmol硝酸锰和0.1 mmol硝酸铕溶于3mL乙腈、6mL二甲基甲酰胺和6mL水的混合溶剂当中，在室温下搅拌形成混合液A，然后将上述混合液A在75℃下回流6小时得到混合液B，再将所述混合液B置入25 mL水热反应釜中在溶剂热180℃条件下加热反应24小时后以4℃/小时降至室温得到所述的白光荧光粉。本实施例的荧光光谱图如实施例1所示。
实施例
3
将0.1 mmol1,4-二(咪唑-1-基)苯、0.2 mmol2,2'-二甲氧基-4,4'-联苯基二羧酸、0.1 mmol硝酸锰和0.1 mmol硝酸铕溶于3mL乙腈、6mL二甲基甲酰胺和6mL水的混合溶剂当中，在室温下搅拌形成混合液A，然后将上述混合液A在75℃下回流6小时得到混合液B，再将所述混合液B置入25 mL水热反应釜中在溶剂热170℃条件下加热反应36小时后以2℃/小时降至室温得到所述的白光荧光粉。本实施例的荧光光谱图如实施例1所示。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制，但凡采用等同替换或等效变换的形式所获得的技术方案，均应落在本发明的保护范围之内。
Claims (1)
1.一种LED用白光荧光粉，其特征在于：该荧光粉的化学分子式为C44H34N4O12MnEu，所述荧光粉为三斜晶系，P-1空间群，晶胞参数为a=21.329(2) Å，b=18.527(2) Å，c=23.048(3) Å，α=105.38(3) º，β=101.17(7)
º，γ=106.39(2) º，V=9107.7 (1) Å3；
其中，所述白光荧光粉由如下方法制备：将有机化合物1,4-二(咪唑-1-基)苯、2,2'-二甲氧基-4,4'-联苯基二羧酸、硝酸锰、硝酸铕加入至乙腈、二甲基甲酰胺和水的混合溶剂当中，在室温下搅拌形成混合液A，然后将混合液A在75℃下回流6小时得到混合液B，再将混合液B在溶剂热条件下加热反应后缓慢降温得到所述白光荧光粉；
所述溶剂热的加热反应温度为160℃~180℃，所述溶剂热的加热反应时间为24~48小时，所述溶剂热反应后的降温为2℃/小时~5℃/小时降至室温，所述1,4-二(咪唑-1-基)苯、2,2'-二甲氧基-4,4'-联苯基二羧酸、硝酸锰、硝酸铕的摩尔比为1:2:1:1，所述乙腈、二甲基甲酰胺和水的体积比选为1:2:2。
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