Ca2Si（O4-xNx）：Eu2+绿色荧光粉的制备及其发光性能

周仁迪; 黄雪飞; 齐智坚; 黄维刚

doi:10.7498/aps.63.197801

摘要

利用在Ca-Si-O干凝胶前驱体中添加Si3N4的方法于非还原气氛下合成了含N固溶体Ca2Si（O4-xNx）：Eu2+绿色荧光粉. 通过X射线衍射仪、扫描电子显微镜以及荧光分光光度计分别分析了产物的物相结构、颗粒形貌和发光性能. 结果显示，Si3N4与前驱体的混合物在非还原气氛（纯氮气）下于1100℃焙烧后获得含N固溶体Ca2Si（O4-xNx）：Eu2+荧光粉，特别是其中Eu3+被还原为Eu2+，产物的晶体结构与βup -Ca2SiO4相一致. Ca2Si（O4-xNx）：Eu2+能够被270–400 nm 范围内的紫外线有效激发，其发射光谱呈宽带发射. 随着N含量的增加，发射峰出现一定程度红移（501–504 nm），而且发光强度显著提高. 当Eu2+浓度为0.25 mol%时发光强度达最大值，浓度超过0.25 mol%时，发光强度显著降低，出现浓度猝灭效应.

关键词:

白光LED /
荧光粉 /
溶胶凝胶法 /
Si3N4

Abstract

A nitrogen-contained solid solution Ca2Si(O4-xNx):Eu2+ green phosphors was successfully synthesized using the method of mixing Ca-Si-O xerogel precursor with Si3N4 powders in a non-reducing atmosphere (pure nitrogen). The structure, morphology, and luminescent properties of the phosphors are characterized by X-ray diffraction (XRD), \text {scanning} electron microscopy (SEM) and photoluminescence (PL) spectra. Results show that the Ca2Si(O4-xNx):Eu2+ is obtained and especially the reduction of Eu3+ to Eu2+ occurs when the mixture of Si3N4 and precursor is calcined at 1100℃ in pure nitrogen atmosphere. XRD results show that the crystalline structure of N-contained solid solution Ca2Si(O4-xNx):Eu2+ is consistent with that of βup -Ca2SiO4 phase. The phosphors can be efficiently excited at a wavelength of 270–400 nm and shows a single intense broadband emission (450–600 nm). Significantly, the red-shift (501 nm to 504 nm) of emission peak occurs and the luminescent intensity is improved significantly with increasing N concentration. With increasing Eu2+ concentration, luminescent intensity of the phosphors increases continuously and reaches a maximum value at the concentration of 0.25 mol% Eu2+. Then the luminescent intensity decreases significantly and the concentration quenching effect appears when Eu2+ concentration is above 0.25 mol%.

Keywords:

white LED /
phosphors /
sol-gel method /
Si3N4

作者及机构信息

1.
四川大学材料科学与工程学院, 成都 610065

基金项目: 四川省科技支撑项目（批准号：2008GZ0173）资助的课题.

Authors and contacts

1.
College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China

Funds: Project supported by the Scientific Research Foundation of the Science & Technology Department of Sichuan Province, China (Grant No. 2008GZ0173 ).

参考文献

[1]	Zhang X H, Lu Z M, Meng F B, Lu F, Hu L, Xu X W, Tang C C 2012 Mater. Lett. 66 16
[2]	Chen Y, Zhang J, Zhang L, Han P D, Wang L X, Zhang Q T 2012 Rare Matals. 31 479
[3]	Yu Y, Liu Z J, Chen Q Q, Dai N L, Li J Y, Yang L Y 2013 Acta Phys. Sin. 62 017804(in Chinese) [余阳, 刘自军, 陈乔乔, 戴能利, 李进延, 杨旅云 2013 物理学报 62 017804]
[4]	Li K, Shen C Y 2012 Appl. Opt. 123 621
[5]	Kuo C H, Sheu J K, Chang S J, Su Y K, Wu L W, Tsai J M, Liu C H, Wu R K 2003 Jpn. J. App. Phys. 42 2284
[6]	Li P L, Yang Z P, Wang Z L, Guo Q L 2008 Chin. Phys. B 17 1137
[7]	Qi Z J, Huang W G 2013 Acta Phys. Sin. 62 197801(in Chinese) [齐智坚, 黄维刚 2013 物理学报 62 197801]
[8]	Zhang X, Fei Q N, Mao Z Y, Liu Y H, Cai Y, Lu Q F, Tian H, Wang D J 2011 J. Rare Earths 29 522
[9]	Wu Y, Wang Y S, He D W, Fu M, Chen W Y, Li Y, Mao F 2011 Spectrosc. Spec. Anal. 31 890(in Chinese) [邬洋, 王永生, 何大伟, 富鸣, 陈震旻, 李玥, 苗峰 2011 光谱学与光谱分析 31 890]
[10]	Li P L, Wang Z J, Yang Z P, Guo Q L, Li X 2009 J. Chin. Ceram. Soc. 37 462
[11]	Choi N S, Park K W, Park B W, Zhang X M, Kim J S, Kung P, Kim S M 2010 J. Lumin. 130 560
[12]	Yang Z P, Liu Y F 2006 Acta Phys.Sin. 55 4946(in Chinese) [杨志平, 刘玉峰 2006 物理学报 55 4946]
[13]	Yang Z P, Tian J, Li X, Yang G W, Wang S L, Li P L 2008 J. Synth. Cryst. 37 368(in Chinese) [杨志平, 田晶, 李旭, 杨广伟, 王少丽, 李盼来 2008 人工晶体学报 37 368]
[14]	Liu Y H, Mao Z Y, Yu W H, Lu Q F, Wang D J 2010 J. Alloys Comp. 493 406
[15]	Gu Y X, Zhang Q H, Li Y G, Wang H Z 2011 J. Alloys Comp. 509 L109
[16]	Li P L, Yang Z P, Wang Z J, Xiong Z J, Guo Q L 2008 Acta Phys. Chim. Sin. 24 179(in Chinese) [李盼来, 杨志平, 王志军, 熊志军, 郭庆林 2008 物理化学学报 24 179]
[17]	Luo Y Y, Jo D S, Senthil K, Tezuka S, Kakihana M, Toda K, Masaki T, Yoon D H 2012 J. Solid State Chem. 189 68
[18]	Wang Z J, Li P L, Wang G, Yang Z P, Guo Q L 2008 Acta Phys. Sin. 57 4575(in Chinese) [王志军, 李盼来, 王刚, 杨志平, 郭庆林 2008 物理学报 57 4575]
[19]	Zheng X, Fei Q N, Mao Z Y, Liu Y H, Cai Y, Lu Q F, Tian H, Wang D J 2011 J. Rare Earths 29 522
[20]	Zhang M, He X, Ding W J, Wang J 2010 Prog. Chem. 22 376(in Chinese) [张梅, 何鑫, 丁维嘉, 王静 2010 化学进展 22 376]
[21]	Su Q, Zeng Q H, Pei Z W 2000 Chin. J. Inorg. Chem. 16 293(in Chinese) [苏锵, 曾庆华, 裴治武 2000 无机化学学报 16 293]
[22]	Li J Y 2003 Rare Earth Luminescent Material and Applications (Beijing: Chemical Industry Press) pp3-4 (in Chinese) [李建宇 2000 稀土发光材料及其应用(北京: 化学化工出版社)第3–4页]
[23]	Choi S W, Hong S H, Kim Y J 2009 J. Am. Ceram. Soc. 92 2025

施引文献

[1]	Zhang X H, Lu Z M, Meng F B, Lu F, Hu L, Xu X W, Tang C C 2012 Mater. Lett. 66 16
[2]	Chen Y, Zhang J, Zhang L, Han P D, Wang L X, Zhang Q T 2012 Rare Matals. 31 479
[3]	Yu Y, Liu Z J, Chen Q Q, Dai N L, Li J Y, Yang L Y 2013 Acta Phys. Sin. 62 017804(in Chinese) [余阳, 刘自军, 陈乔乔, 戴能利, 李进延, 杨旅云 2013 物理学报 62 017804]
[4]	Li K, Shen C Y 2012 Appl. Opt. 123 621
[5]	Kuo C H, Sheu J K, Chang S J, Su Y K, Wu L W, Tsai J M, Liu C H, Wu R K 2003 Jpn. J. App. Phys. 42 2284
[6]	Li P L, Yang Z P, Wang Z L, Guo Q L 2008 Chin. Phys. B 17 1137
[7]	Qi Z J, Huang W G 2013 Acta Phys. Sin. 62 197801(in Chinese) [齐智坚, 黄维刚 2013 物理学报 62 197801]
[8]	Zhang X, Fei Q N, Mao Z Y, Liu Y H, Cai Y, Lu Q F, Tian H, Wang D J 2011 J. Rare Earths 29 522
[9]	Wu Y, Wang Y S, He D W, Fu M, Chen W Y, Li Y, Mao F 2011 Spectrosc. Spec. Anal. 31 890(in Chinese) [邬洋, 王永生, 何大伟, 富鸣, 陈震旻, 李玥, 苗峰 2011 光谱学与光谱分析 31 890]
[10]	Li P L, Wang Z J, Yang Z P, Guo Q L, Li X 2009 J. Chin. Ceram. Soc. 37 462
[11]	Choi N S, Park K W, Park B W, Zhang X M, Kim J S, Kung P, Kim S M 2010 J. Lumin. 130 560
[12]	Yang Z P, Liu Y F 2006 Acta Phys.Sin. 55 4946(in Chinese) [杨志平, 刘玉峰 2006 物理学报 55 4946]
[13]	Yang Z P, Tian J, Li X, Yang G W, Wang S L, Li P L 2008 J. Synth. Cryst. 37 368(in Chinese) [杨志平, 田晶, 李旭, 杨广伟, 王少丽, 李盼来 2008 人工晶体学报 37 368]
[14]	Liu Y H, Mao Z Y, Yu W H, Lu Q F, Wang D J 2010 J. Alloys Comp. 493 406
[15]	Gu Y X, Zhang Q H, Li Y G, Wang H Z 2011 J. Alloys Comp. 509 L109
[16]	Li P L, Yang Z P, Wang Z J, Xiong Z J, Guo Q L 2008 Acta Phys. Chim. Sin. 24 179(in Chinese) [李盼来, 杨志平, 王志军, 熊志军, 郭庆林 2008 物理化学学报 24 179]
[17]	Luo Y Y, Jo D S, Senthil K, Tezuka S, Kakihana M, Toda K, Masaki T, Yoon D H 2012 J. Solid State Chem. 189 68
[18]	Wang Z J, Li P L, Wang G, Yang Z P, Guo Q L 2008 Acta Phys. Sin. 57 4575(in Chinese) [王志军, 李盼来, 王刚, 杨志平, 郭庆林 2008 物理学报 57 4575]
[19]	Zheng X, Fei Q N, Mao Z Y, Liu Y H, Cai Y, Lu Q F, Tian H, Wang D J 2011 J. Rare Earths 29 522
[20]	Zhang M, He X, Ding W J, Wang J 2010 Prog. Chem. 22 376(in Chinese) [张梅, 何鑫, 丁维嘉, 王静 2010 化学进展 22 376]
[21]	Su Q, Zeng Q H, Pei Z W 2000 Chin. J. Inorg. Chem. 16 293(in Chinese) [苏锵, 曾庆华, 裴治武 2000 无机化学学报 16 293]
[22]	Li J Y 2003 Rare Earth Luminescent Material and Applications (Beijing: Chemical Industry Press) pp3-4 (in Chinese) [李建宇 2000 稀土发光材料及其应用(北京: 化学化工出版社)第3–4页]
[23]	Choi S W, Hong S H, Kim Y J 2009 J. Am. Ceram. Soc. 92 2025

计量

文章访问数: 5208
PDF下载量: 968
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板