CaSi2O2N2:Ce/Tb、Eu叠层纤维膜的制备及其荧光性能研究

doi:10.15541/jim20170227

无机材料学报 ›› 2018, Vol. 33 ›› Issue (4): 403-408.DOI: 10.15541/jim20170227

CaSi₂O₂N₂:Ce/Tb、Eu叠层纤维膜的制备及其荧光性能研究

崔博¹, 贾巍², 陈振华¹, 李耀刚¹, 张青红¹, 王宏志¹

1. 东华大学材料科学与工程学院, 纤维材料改性国家重点实验室, 上海 201620;
2. 上海空间电源研究所, 上海 200245

收稿日期:2017-05-08 修回日期:2017-07-16 出版日期:2018-04-30 网络出版日期:2018-03-27
作者简介:崔博(1986-), 男, 博士研究生. E-mail: cui2005bo@126.com
基金资助:
国家自然科学基金(51572046, 51603037);高等学校学科创新引智计划(111-2-04);上海市自然科学基金(15ZR1401200);上海市优秀学术带头人(16XD1400100);上海高校特聘教授(东方学者)岗位计划

Synthesis and Property of CaSi₂O₂N₂:Ce/Tb, Eu Stacking Luminescence Fibers

CUI Bo¹, JIA Wei², CHEN Zheng-Hua¹, LI Yao-Gang¹, ZHANG Qing-Hong¹, WANG Hong-Zhi¹

1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China;
2. Shanghai Institute of Space Power-sources, Shanghai 200245, China

Received:2017-05-08 Revised:2017-07-16 Published:2018-04-30 Online:2018-03-27
About author:CUI Bo. E-mail: cui2005bo@126.com
Supported by:
National Natural Science Foundation of China (51572046, 51603037);The Program of Introduction Talents of Discipline to Universities (111-2-04);Natural Science Foundation of Shanghai (15ZR1401200);Program of Shanghai Academic Research Leader (16XD1400100);The Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning.

摘要/Abstract

摘要：

采用分步静电纺丝与气相还原氮化相结合的方法, 通过控制纺丝液的组成和纺丝时间, 制备了用于白光LED的CaSi₂O₂N₂:Ce/Tb、Eu叠层荧光纤维膜。采用SEM、TEM、XRD和PL等对材料进行了表征。样品在宏观上呈现完整薄膜状态, 微观上保持纤维结构, TEM照片显示荧光纤维由小晶粒组成。XRD分析结果表明: 1300℃氮化1 h可以得到CaSi₂O₂N₂晶型, 稀土离子的掺入没有改变CaSi₂O₂N₂的主晶相。在近紫外激发光照射下, CaSi₂O₂N₂:Ce/Tb、Eu叠层纤维膜两侧具有不同发射光。激发光照射Eu离子掺杂面能够降低叠层纤维膜的发射光重复吸收。将制备的CaSi₂O₂N₂:Ce/Tb、Eu叠层荧光纤维膜封装于近紫外激发的LED芯片中, 可以实现白光发射。

关键词: 叠层结构, 静电纺丝, 荧光纤维, 氮氧化物

Abstract:

By adjusting composition of spinning solution and spinning time, CaSi₂O₂N₂:Ce/Tb, Eu stacking fluorescent fibers for white LEDs were prepared through multi-step electrospinning and gas-reduction procedures. The obtained samples were characterized by SEM, TEM, XRD, and PL. The obtained sample keeps fiber morphology, and assembles as film at macro level. TEM images show that the fluorescent fibers consist of nanocrystalline. XRD patterns demonstrate that CaSi₂O₂N₂ crystal can be prepared through nitridizing at 1300℃ for 1 h, and its phase can be maintained after doping CeTb/Eu ions. Both sides of the CaSi₂O₂N₂:Ce/Tb, Eu stacking fluorescent fiber mats emit different light under the N-UV excitation light. The Eu ion doping side exposed to the exciting light can effectively undercut the emitting light reabsorption process of the fiber-stacking mat. It demonstrates that white light will be emitted when CaSi₂O₂N₂:Ce/Tb, Eu fluorescent fiber stacking mats are applied in a white light emitting diodes with N-UV chip.

Key words: stacking structure, electrospinning, luminescence fiber, oxynitride

中图分类号:

TB34

崔博, 贾巍, 陈振华, 李耀刚, 张青红, 王宏志. CaSi₂O₂N₂:Ce/Tb、Eu叠层纤维膜的制备及其荧光性能研究[J]. 无机材料学报, 2018, 33(4): 403-408.

CUI Bo, JIA Wei, CHEN Zheng-Hua, LI Yao-Gang, ZHANG Qing-Hong, WANG Hong-Zhi. Synthesis and Property of CaSi₂O₂N₂:Ce/Tb, Eu Stacking Luminescence Fibers[J]. Journal of Inorganic Materials, 2018, 33(4): 403-408.

图/表 10

图1 (a)原始纤维膜和(b)去除PVP模板后样品的SEM照片

Fig. 1 SEM images of as-formed fiber precursor (a) and the samples after removing the organic template (b)

图2 氮化后CaSi2O2N2纤维膜的SEM照片(a), TEM照片(b), 截面SEM照片(c)和叠层荧光纤维膜示意图(d), 插图为荧光膜在紫外光照射下的数码照片

Fig. 2 SEM image of as-prepared CaSi2O2N2 fiber mats (a), TEM image (b) and cross section SEM image (c), the illustrative scheme for the stacking fiber mats (d) with inset showing the photo of the fiber films under ultraviolet light

图3 CaSi2O2N2叠层荧光膜不同掺杂面的XRD图谱与CaSi2O2N2标准XRD图谱(PDF 44-0117)

Fig. 3 XRD patterns of CaSi2O2N2 phosphors doping with Ce/Tb, Eu and standard XRD pattern (PDF 44-0117)

图4 CaSi2O2N2:Ce3+, CaSi2O2N2:Tb3+纤维膜的激发与发射光谱(a), CaSi2O2N2:Ce3+/Tb3+、Eu2+纤维膜中Ce3+/Tb3+掺杂面(b)和Eu2+掺杂面(c)的激发与发射光谱, 插图为荧光膜在紫外光照射下的数码照片

Fig. 4 Excitation and emission spectra of CaSi2O2N2:Ce3+, CaSi2O2N2:Tb3+ fiber mats (a), Ce3+/Tb3+ side (b) and Eu2+ side (c) of CaSi2O2N2:Ce3+/Tb3+, Eu2+ fiber mats with inset showing the photo of the fiber films under the ultraviolet light

图5 荧光膜发光性能测试光路示意图

Fig. 5 Schematic illustration for luminescence measurement of films

图6 传统法和透射法测到的CaSi2O2N2:Ce3+/Tb3+、Eu2+叠层纤维膜, 激发光照射Ce3+/Tb3+掺杂面(a)、(b); 激发光照射Eu2+掺杂面(c)、(d)的激发与发射光谱

Fig. 6 Excitation and emission spectra of Ce3+/Tb3+ side (a), (b) and Eu2+ side (c), (d) of CaSi2O2N2:Ce3+/Tb3+, Eu2+ fiber mats tested by reflection test and transmission test

图7 照射叠层荧光纤维膜Ce/Tb离子掺杂面(a)和Eu离子掺杂面(b)的发射光谱

Fig. 7 Emission spectra of stacking structure fiber mats excitaed on Ce/Tb side (a) and Eu side (b)

图8 Ce/Tb离子、Eu离子掺杂面厚度相同时叠层纤维膜的发射光谱以及Ce/Tb、Eu离子掺杂纤维混合膜的发射光谱

Fig. 8 Emission spectra of CaSi2O2N2:Ce3+/Tb3+, Eu2+ stacking fiber mats and Ce3+/Tb, Eu fiber blend mats

表1 不同层间比CaSi2O2N2 : Ce3+/Tb3+, Eu2+叠层荧光纤维膜封装LED的光学性能

Table 1 Electroluminescence properties of LED lamps using CaSi2O2N2 : Ce3+/Tb3+, Eu2+ fiber mats

Thickness ratio (Ce/Tb:Eu)	Correlated color temperature/K	CIE value (x, y)
4 : 1	11674	(0.2594, 0.3019)
1 : 1	5674	(0.3284, 0.3456)
1 : 4	3740	(0.4388, 0.5230)

图9 CaSi2O2N2: Ce3+/Tb3+、Eu2+叠层纤维膜的CIE坐标, 以及封装紫外光LED的数码照片

Fig. 9 CIE chromaticity coordinates of CaSi2O2N2:Ce3+/Tb3+, Eu2+ samples. The lighting pictures of three LEDs with CaSi2O2N2:Ce3+/Tb3+, Eu2+ fiber mats at a drive current of 100 mA

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CaSi₂O₂N₂:Ce/Tb、Eu叠层纤维膜的制备及其荧光性能研究

Synthesis and Property of CaSi₂O₂N₂:Ce/Tb, Eu Stacking Luminescence Fibers

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