Sm3+掺杂NaLa(WO4)2单一基质白光荧光粉制备及发光性能

姜洪喜; 吕树臣

doi:10.7498/aps.70.20210493

摘要

单离子掺杂体系单一基质白光荧光粉可以有效克服紫外芯片+三基色荧光粉获得白光方案中颗粒分散性和沉降性不均的问题, 克服荧光粉彼此间发光再吸收及三基色配比调控等问题. 本文采用熔融盐法制备了Sm³⁺离子单掺NaLa(WO₄)₂:x Sm³⁺白光荧光粉. 在紫外光激发下, ${\rm{WO}}_{4}^{2-}$自激活发出的蓝绿光, 与Sm³⁺发射的绿光、黄光、橙光和红光混合得到了白光. 在250 nm激发下, 荧光粉会发出冷白光; 在403 nm激发下会发出暖白光. 随着Sm³⁺掺杂浓度增加, 相对色温逐渐降低. 所制备的样品均为纯的四方相结构, 晶粒形貌为不规则菱形薄片. 通过分析实验数据确定Sm³⁺离子间的能量猝灭类型为电偶极-电偶极作用. 得到的NaLa(WO₄)₂: x Sm³⁺荧光粉具有较高的稳定性, 能被近紫外LED芯片有效地激发, 可作为单离子掺杂单一基质白光荧光粉潜在候选.

关键词:

Abstract

Single ion doped single phase white emitting phosphors have some special advantages and great potential applications in the field of high quality LED lighting. This type of phosphors can effectively solve the problem of uneven particle dispersion and sedimentation in the white light scheme obtained by UV chip plus trichromatic phosphor, and solve the problems of the luminescence and reabsorption between phosphors and the regulation of trichromatic ratio. A comparison of the single-ion doping luminescent material with the multi-ion doping system shows that the single-ion doping luminescent material is simpler in both preparation process and luminescence color adjustment, which can achieve higher color rendering index, more easily controlled color temperature and closer to the color coordinates of white light. According to the principle of colorimetry and luminescence, light of two or more wavelengths may be combined to obtain white light emission. Under the UV excitation, the Sm³⁺ ions emit relatively strong green, yellow, orange and red light at 580–670 nm. Under UV excitation, the broadband spectrum of ${\rm{WO}}_{4}^{2-} $ self-activated emission covers almost the whole visible region, but the blue-green light is strong in the short wavelength region and the yellow-orange-red light is weak in the long wavelength region. When Sm³⁺ ions are doped into tungstate, Sm³⁺ ions’ luminescence can effectively supplement the weak luminescence intensity of tungstate in the long-wave region, and white light can be obtained. Under the excitation of 250 nm, the phosphor emits cold white light, and warm white light under the excitation of 403 nm. The experimental results show that Sm³⁺ ions have a significant effect on the correlated color temperature adjustment of self-activated luminescence of NLW phosphors. All the prepared samples are crystallized into the tetragonal crystal phase structures and that their morphologies present rhombic sheet. By analyzing the experimental data, the type of energy transfer between Sm³⁺ ions is determined to be electrical dipole–electrical dipole interaction. The NLW: xSm³⁺ phosphor has high stability and can be effectively excited by ultraviolet/near-ultraviolet light, which can be used as a potential candidate of single matrix single-ion doped white phosphors.

Keywords:

作者及机构信息

姜洪喜^1,2,
吕树臣^1,3

1.
哈尔滨工程大学物理与光电工程学院, 哈尔滨　150001

2.
黑龙江科技大学理学院, 哈尔滨　150027

3.
哈尔滨师范大学, 光电带隙材料教育部重点实验室, 哈尔滨　150025

通信作者: 吕树臣, hsdlsc63@126.com

Authors and contacts

1.
College of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, China

2.
College of Science, Heilongjiang University of Science and Technology, Harbin 150027, China

3.
Key Laboratory of Photoelectric Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, China

Corresponding author: Lü Shu-Chen, hsdlsc63@126.com

文章全文 : translate this paragraph

参考文献

[1]	郭伟玲, 邓杰, 王嘉露, 王乐, 邰建鹏 2019 68 247303 Google Scholar Guo W L, Deng J, Wang J L, Wang L, Tai J P 2019 Acta Phys. Sin. 68 247303 Google Scholar
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[3]	苏小娜, 万英, 周芷萱, 胡莲莲 2017 66 230701 Google Scholar Su X N, Wan Y, Zhou Z X, Hu L L 2017 Acta Phys. Sin. 66 230701 Google Scholar
[4]	Jiang G C, Wei X T, Chen Y H, Duan C K, Yin M, Yang B, Cao W W 2015 Mater. Lett. 143 98 Google Scholar
[5]	Du P, Wu Y F, Yu J S 2018 RSC Adv. 12 6419 Google Scholar
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[7]	Du P, Huang X Y, Yu J S 2018 Chem. Eng. J. 337 91 Google Scholar
[8]	梁思思, 尚蒙蒙, 林君 2018 物理化学学报 34 237 Google Scholar Liang S S, Shang M M, Lin J 2018 Acta Phys-Chem. Sin. 34 237 Google Scholar
[9]	曹逊, 曹翠翠, 孙光耀, 金平实 2019 无机材料学报 34 1145 Google Scholar Cao X, Cao C C, Sun G Y, Jin P S 2019 J. Inorg. Mater. 34 1145 Google Scholar
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[18]	刘艳, 姜莹莹, 刘桂霞, 王进贤 2013 无机化学学报 29 277 Google Scholar Liu Y, Jiang Y Y, Liu G X, Wang J X 2013 Inorg. Chem. 29 277 Google Scholar
[19]	Du P, Wu S Q, Yu J S 2016 J. Lumin. 173 192 Google Scholar
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[21]	Li L L, Yang X Y, Li J Q, et al. 2020 J. Lumin. 173 117377 Google Scholar
[22]	毕长虹, 孟庆裕 2013 19 197804 Google Scholar Bi C H, Meng Q Y 2013 Acta Phys. Sin. 19 197804 Google Scholar
[23]	Chanu T T T, Singh N R 2016 J. Mater. Sci-Mater. El. 28 3909 Google Scholar
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[25]	Cao R P, Xu H D, Peng D D, Jiang S H 2015 Supperlattice Microst. 88 5 Google Scholar
[26]	Zhai Y Q, Wang M, Zhao Q, Yang H L, Ding H H 2016 J. Mater. Sci-Mater. El. 27 279 Google Scholar
[27]	Durirajan A, Balaji D, Kavi Rasu K, et al. 2016 J. Lumin. 170 743 Google Scholar
[28]	陈炳炎, 刘粤惠, 陈东丹, 姜中宏 2005 54 3418 Google Scholar Chen B Y, Liu Y H, Chen D D, Jiang Z H 2005 Acta Phys. Sin. 54 3418 Google Scholar
[29]	孟庆裕, 刘志鑫, 孙文军 2013 62 097801 Google Scholar Meng Q Y, Liu Z X, Sun W J 2013 Acta Phys. Sin. 62 097801 Google Scholar
[30]	Dexter D L, Schulman J H 1954 J. Chem. Phys. 22 1063 Google Scholar

施引文献

图 1 晶体结构信息　(a) NLW:x Sm³⁺荧光粉的XRD谱; (b) (112)峰位置随Sm³⁺浓度变化偏移; (c) NLW:2%Sm³⁺ XRD谱的Rietveld精修; (d) NLW:x Sm³⁺晶体结构图

Fig. 1. Crystal structure information: (a) XRD patterns of NLW:x Sm³⁺ phosphors; (b) offset of the (112) peak position with the Sm³⁺ concentration; (c) rietveld refinement of XRD pattern of NLW:2%Sm³⁺; (d) the crystal structure of NLW:x Sm³⁺.

下载: 全尺寸图片幻灯片

图 2 NLW:2%Sm³⁺样品的表征　(a) SEM; (b) EDS; (c)−(g) 元素Mapping

Fig. 2. Characterization of NLW:2%Sm³⁺ sample: (a) SEM; (b) EDS; (c)−(g) element mapping.

下载: 全尺寸图片幻灯片

图 3 样品NLW:2%Sm³⁺激发光谱

Fig. 3. Excitation spectrum of NLW:2%Sm³⁺.

下载: 全尺寸图片幻灯片

图 4 样品在403 nm激发下发射谱　(a) NLW:x Sm³⁺(x = 1%−5%); (b) NLW:2%Sm³⁺

Fig. 4. Emission spectra excited at 403 nm: (a) NLW:x Sm³⁺ (x = 1%−5%); (b) NLW:2%Sm³⁺.

下载: 全尺寸图片幻灯片

图 5 样品在250 nm激发下发射谱　(a) NLW:x Sm³⁺(x = 1%−5%); (b) NLW:2%Sm³⁺发射谱的宽带峰拟合; (c) NLW:2%Sm³⁺渲染图

Fig. 5. Emission spectra excited at 250 nm: (a) NLW:x Sm³⁺ (x = 1%−5%); (b) fitting broad band peak of emission spectrum of NLW:2%Sm³⁺; (c) rendering picture of NLW:2%Sm³⁺.

下载: 全尺寸图片幻灯片

图 6 样品NLW:x Sm³⁺的色度图与色坐标　(a) 250 nm激发下; (b) 403 nm激发下

Fig. 6. Chromaticity diagrams and color coordinates of NLW:x Sm³⁺: (a) Excited at 250 nm; (b) excited at 403 nm.

下载: 全尺寸图片幻灯片

图 7 ${\rm{WO}}_{4}^{2-} $向Sm³⁺能量转移过程

Fig. 7. Energy transfer process from ${\rm{WO}}_{4}^{2-} $to Sm³⁺.

下载: 全尺寸图片幻灯片

图 8 系列样品NLW:x Sm³⁺中Sm³⁺的衰减曲线与荧光寿命

Fig. 8. Decay curves and fluorescence lifetimes of Sm³⁺ in series NLW:x Sm³⁺ sample.

下载: 全尺寸图片幻灯片

图 9 NLW:x Sm³⁺的lg(I/x)与lg(x)关系曲线

Fig. 9. Curve of lg(I/x) versus lg(x) for NLW:x Sm³⁺.

下载: 全尺寸图片幻灯片

表 1 NLW:x Sm³⁺晶格参数

Table 1. Lattice constants of NLW:x Sm³⁺.

NLW:xSm³⁺ concentrations	a/Å	c/Å	unit cell volume/Å³
1%	5.542	11.692	359.1
2%	5.539	11.699	358.9
3%	5.531	11.692	357.7
4%	5.530	11.691	357.5
5%	5.528	11.690	357.2

下载: 导出CSV

表 2 在403 nm激发下NLW:x Sm³⁺的I₆₄₄/I₆₀₄比值

Table 2. Ratios of I₆₄₄ to I₆₀₄ of NLW:x Sm³⁺ excited at 403 nm.

Sm³⁺ concentrations/%	1	2	3	4	5
I₆₄₄/I₆₀₄	0.93	1.07	1.05	1.04	1.02

下载: 导出CSV

表 3 NLW:x Sm³⁺色坐标和相对色温

Table 3. Color coordinates and relative color temperatures of NLW:x Sm³⁺ samples.

Sm³⁺ concentrations/%	1	2	3	4	5
λ_ex = 250 nm	(0.270, 0.249) 16618 K	(0.287, 0.248) 12435 K	(0.288, 0.258) 11032 K	(0.283, 0.255) 12346 K	(0.313, 0.280) 6971 K
λ_ex = 403 nm	(0.298, 0.251) 9963 K	(0.374, 0.286) 3057 K	(0.377, 0.282) 2911 K	(0.376, 0.286) 3004 K	(0.357, 0.279) 3798 K

下载: 导出CSV

map

[1]	郭伟玲, 邓杰, 王嘉露, 王乐, 邰建鹏 2019 68 247303 Google Scholar Guo W L, Deng J, Wang J L, Wang L, Tai J P 2019 Acta Phys. Sin. 68 247303 Google Scholar
[2]	Xia H, Lei L, Hong W Q, Xu S Q 2018 J. Alloy Compd. 757 239 Google Scholar
[3]	苏小娜, 万英, 周芷萱, 胡莲莲 2017 66 230701 Google Scholar Su X N, Wan Y, Zhou Z X, Hu L L 2017 Acta Phys. Sin. 66 230701 Google Scholar
[4]	Jiang G C, Wei X T, Chen Y H, Duan C K, Yin M, Yang B, Cao W W 2015 Mater. Lett. 143 98 Google Scholar
[5]	Du P, Wu Y F, Yu J S 2018 RSC Adv. 12 6419 Google Scholar
[6]	Du P, Yu J S 2016 Mater. Res. Bull. 84 303 Google Scholar
[7]	Du P, Huang X Y, Yu J S 2018 Chem. Eng. J. 337 91 Google Scholar
[8]	梁思思, 尚蒙蒙, 林君 2018 物理化学学报 34 237 Google Scholar Liang S S, Shang M M, Lin J 2018 Acta Phys-Chem. Sin. 34 237 Google Scholar
[9]	曹逊, 曹翠翠, 孙光耀, 金平实 2019 无机材料学报 34 1145 Google Scholar Cao X, Cao C C, Sun G Y, Jin P S 2019 J. Inorg. Mater. 34 1145 Google Scholar
[10]	Tian L, Wang L X, Zhang L, Zhang Q T, Ding W H, Yu M X 2015 J. Mater. Sci-Mater El. 26 8507 Google Scholar
[11]	Hsu C H, Das S, Lu C H 2012 J. Electro. Chem. Soc. 159 193 Google Scholar
[12]	Meng J X, Yang C T, Chen Q Q 2010 J. Lumin. 130 1320 Google Scholar
[13]	Wu Z C, Liu J, Hou W G 2010 J. Alloy Compd. 498 139 Google Scholar
[14]	Du P, Yu J S 2017 Dyes. Pigments. 147 16 Google Scholar
[15]	Luwang M N, Ningthoujam R S, Srivastava S K 2011 J. Mater. Chem. 21 5326 Google Scholar
[16]	任艳东, 吕树臣 2011 60 087804 Google Scholar Ren Y D, Lü S C 2011 Acta Phys. Sin. 60 087804 Google Scholar
[17]	孟庆裕, 李明, 刘林峰, 曲秀荣, 万维龙, 孙江亭 2012 61 107804 Google Scholar Meng Q Y, Li M, Liu L F, Qu X R, Wan W L, Sun J T 2012 Acta Phys. Sin. 61 107804 Google Scholar
[18]	刘艳, 姜莹莹, 刘桂霞, 王进贤 2013 无机化学学报 29 277 Google Scholar Liu Y, Jiang Y Y, Liu G X, Wang J X 2013 Inorg. Chem. 29 277 Google Scholar
[19]	Du P, Wu S Q, Yu J S 2016 J. Lumin. 173 192 Google Scholar
[20]	Jiang H X, Lü S C 2021 Mater. Res. Bull. 135 111123 Google Scholar
[21]	Li L L, Yang X Y, Li J Q, et al. 2020 J. Lumin. 173 117377 Google Scholar
[22]	毕长虹, 孟庆裕 2013 19 197804 Google Scholar Bi C H, Meng Q Y 2013 Acta Phys. Sin. 19 197804 Google Scholar
[23]	Chanu T T T, Singh N R 2016 J. Mater. Sci-Mater. El. 28 3909 Google Scholar
[24]	Liu Y, Liu G X, Dong X T, Wang J X, Yu W S 2014 RSC Adv. 4 58708 Google Scholar
[25]	Cao R P, Xu H D, Peng D D, Jiang S H 2015 Supperlattice Microst. 88 5 Google Scholar
[26]	Zhai Y Q, Wang M, Zhao Q, Yang H L, Ding H H 2016 J. Mater. Sci-Mater. El. 27 279 Google Scholar
[27]	Durirajan A, Balaji D, Kavi Rasu K, et al. 2016 J. Lumin. 170 743 Google Scholar
[28]	陈炳炎, 刘粤惠, 陈东丹, 姜中宏 2005 54 3418 Google Scholar Chen B Y, Liu Y H, Chen D D, Jiang Z H 2005 Acta Phys. Sin. 54 3418 Google Scholar
[29]	孟庆裕, 刘志鑫, 孙文军 2013 62 097801 Google Scholar Meng Q Y, Liu Z X, Sun W J 2013 Acta Phys. Sin. 62 097801 Google Scholar
[30]	Dexter D L, Schulman J H 1954 J. Chem. Phys. 22 1063 Google Scholar

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Sm³⁺掺杂NaLa(WO₄)₂单一基质白光荧光粉制备及发光性能

Synthesis and properties of Sm³⁺ doped NaLa(WO₄)₂ single matrix white phosphors

摘要

Abstract

作者及机构信息

1.
哈尔滨工程大学物理与光电工程学院, 哈尔滨　150001

2.
黑龙江科技大学理学院, 哈尔滨　150027

3.
哈尔滨师范大学, 光电带隙材料教育部重点实验室, 哈尔滨　150025

通信作者: 吕树臣, hsdlsc63@126.com

Authors and contacts

Corresponding author: Lü Shu-Chen, hsdlsc63@126.com

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