Ca0.95Si2O2N2: Eu0.05带状荧光纳米纤维的制备与性能

doi:10.15541/jim20150249

无机材料学报 ›› 2016, Vol. 31 ›› Issue (1): 21-26.DOI: 10.15541/jim20150249

Ca_0.95Si₂O₂N₂: Eu_0.05带状荧光纳米纤维的制备与性能

赵海雷, 崔博, 王宏志, 李耀刚, 张青红

(东华大学纤维材料改性国家重点实验室, 材料科学与工程学院, 上海201620)

收稿日期:2015-05-25 修回日期:2015-07-05 出版日期:2016-01-20 网络出版日期:2015-12-15
作者简介:赵海雷(1987–), 男, 硕士研究生. E-mail: 15026583062@163.com
基金资助:
高等学校学科创新引智计划(111-2-04);高等学校博士学科点专项科研基金(20110075130001);教育部创新团队发展计划(IRT1221);上海市科委项目(12nm0503900, 13JC1400200);硕士研究生学位论文创新基金(EG2015049)

Synthesis and Properties of Nanobelt CaSi₂O₂N₂: Eu_0.05²⁺Fluorescence Fibers

ZHAO Hai-Lei, CUI Bo, WANG Hong-Zhi, LI Yao-Gang, ZHANG Qing-Hong

(State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China)

Received:2015-05-25 Revised:2015-07-05 Published:2016-01-20 Online:2015-12-15
About author:ZHAO Hai-Lei. E-mail: 15026583062@163.com
Supported by:
Program of Introducing Talents of Discipline to Universities (111-2-04);Specialized Research Fund for the Doctoral Program of Higher Education (20110075130001);Innovative Research Team in University (IRT1221);Science and Technology Commission of Shanghai Municipality (12nm0503900, 13JC1400200);Innovation Fund of MSLA (EG2015049)

摘要/Abstract

摘要：

采用静电纺丝与气相还原氮化相结合的方式制备了用于白光LED远场封装的Ca_0.95Si₂O₂N₂: Eu_0.05²⁺带状荧光纤维。通过调节纺丝溶液的配比, 得到了带状结构的Ca-Si-O-Eu前驱体纳米纤维和Ca_0.95Si₂O₂N₂: Eu_0.05²⁺荧光纳米纤维。采用SEM、XRD、PL和HSP-3000 LED光谱测试系统等对材料进行了表征。微观上样品保持了带状纤维结构, 宏观上以薄膜的状态存在, 并具有一定的强度。样品在1250℃下保温4 h后的XRD图谱与CaSi₂O₂N₂的标准卡片相符合, Eu²⁺的掺杂没有改变CaSi₂O₂N₂的晶相。在400 nm激发光的照射下, Eu²⁺掺杂的CaSi₂O₂N₂带状纳米纤维在550 nm附近呈现出一个较宽的来自于Eu²⁺的4f⁶5d→4f⁷跃迁的发射峰。利用Ca_0.95Si₂O₂N₂: Eu²⁺带状荧光纤维膜和蓝光芯片远场封装的白光LED, 具有较低的色温(4832 K), 较高的显色指数(86)和流明效率(125 lm/W)。

关键词: 带状纤维, 静电纺丝, 荧光纤维, 远场封装

Abstract:

Ca_0.95Si₂O₂N₂: Eu_0.05²⁺fluorescent nanobelt fibers for the far field encapsulation of white LEDs were prepared through electrospinning combined with gas-reduction method. By adjusting the ratio of spinning solution, the Ca-Si-O-Eu precursor nanofibers and Ca_0.95Si₂O₂N₂: Eu_0.05²⁺luminescence nanofibers with belt structure were obtained. The obtained samples were characterized by FE-SEM, XRD, PL and HSP-3000 LED test system. The obtained sample not only keeps the morphology of nanobelt fiber but also assembles as film with a certain mechanical strength. XRD patterns of sample nitridized at 1250℃ for 4 h demonstrated that it crystallized well which was assigned to JCPDF card of the CaSi₂O₂N₂crystal, and it maintained CaSi₂O₂N₂phase after doping Eu²⁺ions. Under ultraviolet excitation (400 nm), the emission spectra of Eu²⁺-doped Ca_0.95Si₂O₂N₂sample contains a board peak near 550 nm, which results from Eu²⁺4f⁶5d→4f⁷ transition. Based on the far field encapsulation, white LEDs with low correlated color temperature (4832 K), high-color-rendering index (86) and luminous efficacy of 125 lm/W, were fabricated using the Ca_0.95Si₂O₂N₂: Eu_0.05²⁺ nanobelt fiber mat and blue chip.

Key words: nanobelt fiber, electrospinning, fluorescence fiber, far field encapsulation

中图分类号:

TB34

赵海雷, 崔博, 王宏志, 李耀刚, 张青红. Ca_0.95Si₂O₂N₂: Eu_0.05带状荧光纳米纤维的制备与性能[J]. 无机材料学报, 2016, 31(1): 21-26.

ZHAO Hai-Lei, CUI Bo, WANG Hong-Zhi, LI Yao-Gang, ZHANG Qing-Hong. Synthesis and Properties of Nanobelt CaSi₂O₂N₂: Eu_0.05²⁺Fluorescence Fibers[J]. Journal of Inorganic Materials, 2016, 31(1): 21-26.

图/表 8

图1 热处理前后荧光纤维膜的SEM照片

Fig. 1 SEM images of fibrous membranes before (a) and after (b) heat treatment at 500℃

图2 带状纤维结构的形成机理

Fig. 2 Schematic representation of the formation mechanism of nanobelt fibers

图3 初生纤维膜经过不同温度氮化处理后得到样品的XRD图谱(a), 1250℃氮化后样品的FE-SEM照片(b), 数码照片(c)和紫光灯下发光数码照片(d)

Fig. 3 XRD patterns of the fiber precursor samples nitridized at different temperatures (a) and FE-SEM image (b), digital photo (c), and digital photo under purple light (d) of nanobelt fiber mat after nitridized at 1250℃

图4 初生纤维的热失重(TG)曲线(a)与1250℃氮化后样品的三点弯曲强度曲线(b)

Fig. 4 TGA curves of the fiber precursor sample (a) and strength curve through three point bending test of the nanobelt fiber mat after nitridating under 1250℃

图5 Ca0.95Si2O2N2: Eu0.05荧光纤维膜的激发和发射特征光谱图

Fig. 5 Excitation and emission spectra of Ca0.95Si2O2N2: Eu0.05 nanobelt phosphor fibers

图6 不同温度下氮化(a)和1250℃氮化保温不同时间(b)得到的Ca0.95Si2O2N2: Eu0.05带状荧光纤维膜的激发和发射光谱图

Fig. 6 Photoluminescence spectra of the Ca0.95Si2O2N2: Eu0.05 phosphor fiber mat nitridized at different temperatures (a) and nitridized at 1250℃ for different time (b)

图7 带状荧光纤维膜封装的LEDs发光数码照片及相应的CIE坐标图

Fig. 7 Digital pictures of the LEDs encapsulated with Ca0.95Si2O2N2: Eu0.05 nanobelt phosphor fiber mats and the chromaticity coordinates (a, b) Commercial lighting blue chip; (c, d) Encapsulated LEDs A and B; (e) The chromaticity coordinates

表1 采用Ca0.95Si2O2N2: Eu0.05荧光纤维膜和荧光粉封装LED的荧光特性

Table 1 Electroluminescence properties of LED lamps fabricated with Ca0.95Si2O2N2: Eu0.05 nanobelt phosphor fiber mat and Ca0.95Si2O2N2: Eu0.05 powder

Sample	Correlated color temperature/K	CIE value	Color rendering index	Efficacy/(lm·W^-1)
Phosphor powder	5349	(0.3421, 0.3615)	82	80.5
Sample B	4832	(0.3510, 0.3985)	86	125.0

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Ca_0.95Si₂O₂N₂: Eu_0.05带状荧光纳米纤维的制备与性能

Synthesis and Properties of Nanobelt CaSi₂O₂N₂: Eu_0.05²⁺Fluorescence Fibers

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