Influence of Eu2+ and Dy3+ Concentrations on Fluorescence and Phosphorescence of Sr2MgSi2O7 Phosphors

doi:10.15541/jim20150624

Abstract

Abstract:

Eu²⁺-doped Sr₂MgSi₂O₇ and Eu²⁺ and Dy³⁺ codoped Sr₂MgSi₂O₇ phosphors were synthesized by conventional solid-state reaction. Eu²⁺ and Dy³⁺ concentration effects on the fluorescence and phosphorescence of Sr₂MgSi₂O₇ phosphors were studied. All the samples show a broad emission band centered at about 470 nm, which are ascribed to 4f⁶5d→4f⁷ transition of Eu²⁺ ions. Concentration quenching is found to be the dominant factor decreasing emission intensity and afterglow duration time when Eu²⁺ doping level exceeds the critical concentration. Redshift of the emission bands is also observed as the Eu²⁺ concentration increasing. In order to explain the redshift of the emission bands, the centroid position of 5d level of Eu²⁺, crystal-field splitting energy and Stokes shift are estimated from excitation and emission spectra. Based on the calculation, the redshift of the emission bands mainly results from the variations of crystal-field splitting energy and Stokes shift, but is less influenced by the nephelauxetic effect. The Dy³⁺ ions suppress the fluorescence but enhance the phosphorescence lifetime. When the Dy³⁺ concentration is over 10mol%, the phosphorescence lifetime is shortened, because of concentration quenching of the Eu²⁺\Dy³⁺ ions by the mechanism of tunneling recombination.

Key words: Sr2MgSi2O7, luminescent property, doping, concentration quenching

CLC Number:

TB34

MAO Qi-Nan, LI He, JI Zhen-Guo, XI Jun-Hua, ZHANG Jun, KONG Zhe. Influence of Eu²⁺ and Dy³⁺ Concentrations on Fluorescence and Phosphorescence of Sr₂MgSi₂O₇ Phosphors[J]. Journal of Inorganic Materials, 2016, 31(8): 819-826.

Figures/Tables 12

Fig. 1 XRD patterns of (a) SMS: Eux, (b) SMS: Eux, Dy0.02 and (c) SMS: Eu0.02, Dyy phosphors

Fig. 2 Excitation and emission spectra of SMS: Eux with various Eu2+ concentrationsThe inset in Fig. 2 is the emission spectra of SMS: Eu0.03 under different excitation wavelengths

Fig. 3 Excitation and emission spectra of SMS: Eux, Dy0.02 with various Eu2+ concentrations

Table 1 Emission intensity and wavelength of SMS: Eux and SMS: Eux, Dy0.02 with varied Eu2+concentrations

Concentration (x)		0.01	0.02	0.03	0.04	0.06	0.10
Intensity/(a.u.)	SMS: Eu_x	387	645	710	536	453	257
Intensity/(a.u.)	SMS: Eu_x, Dy_0.02	317	494	621	419	365	165
Wavelength /nm	SMS: Eu_x	470	470	471	471	472	473
Wavelength /nm	SMS: Eu_x, Dy_0.02	470	470	471	471	472	473

Fig. 4 Plots of lg(I/x) versus lg x for SMS: Eux (x≥0.03)Inset shows the emission intensity of SMS: Eux as a function of Eu2+ concentration

Fig. 5 Crystal-field splitting and Stokes shift estimation from the excitation and emission spectra of SMS: Eu0.03 phosphor

Table 2 Centroid of 5d level of Eu2+, crystal-field splitting and Stokes shift in SMS: Eux phosphors

Concentration (x)	0.01	0.02	0.03	0.04	0.06	0.10
Centroid /cm^-1	29550	30190	30130	30150	30140	30130
Crystal-field splitting /cm^-1	12820	12950	12960	13080	13120	13200
Stokes shift /cm^-1	1900	1790	1790	1690	1680	1670

Fig. 6 Excitation and emission spectra of SMS: Eu0.02, Dyy with various Dy3+ concentrations

Fig. 7 Afterglow decay curves of (a) SMS: Eux, Dy0.02 and (b) SMS: Eu0.02, Dyy

Table 3 Variations of decay constants, τ1 and τ2, with Eu2+ concentration in SMS: Eux, Dy0.02

Concentration (x)	0.01	0.02	0.03	0.04	0.06	0.10
τ₁ /s	10.7	11.4	4.5	5.1	3.6	3.1
τ₂ /s	90.6	98.4	41.9	49.3	33.6	19.1

Table 4 Variations of decay constants, τ1 and τ2, with Dy3+ concentration in SMS: Eu0.02, Dyy

Concentration (y)	0	0.01	0.02	0.04	0.06	0.10	0.20
τ₁ /s	6.4	10.3	11.4	13.3	13.8	13.7	12.5
τ₂ /s	48.3	94.1	98.4	129.7	141.1	164.5	138.4

Fig. 8 (a) PL emission intensity and (b) decay constants τ1 and τ2 variations as a function of Eu2+ concentration in SMS: Eux, Dy0.02

References 31

[1]	VAN DEN EECKHOUT K, SMET P F, POELMAN D. Persistent luminescence in Eu2+-doped compounds: a review.Materials, 2010, 3(4): 2536-2566.
[2]	MATSUZAWA T, AOKI Y, TAKEUCHI N, et al.A new long phosphorescent phosphor with high brightness, SrAl2O4: Eu2+, Dy3+.Journal of the Electrochemical Society, 1996, 143(8): 2670-2673.
[3]	KATSUMATA T, NABAE T, SASAJIMA K, et al.Effects of composition on the long phosphorescent SrAl2O4: Eu2+, Dy3+ phosphor crystals.Journal of the Electrochemical Society, 1997, 144(9): L243-L245.
[4]	QIU TAO, JI ZHEN-GUO, KONG ZHE, et al.Preparation and optimization of long persistent luminescent Sr4Al14O25: (Eu, Dy) phosphor materials.Journal of Inorganic Materials, 2012, 27(12): 1341-1344.
[5]	JI ZHENGUO, TIAN SHUN, CHEN WANKE, et al.Enhanced long lasting persistent luminescent SrAl2O4: Eu, Dy ceramics prepared by electron beam bombardment.Radiation Measurement, 2013, 59(59): 210-213.
[6]	WU HAOYI, HU YIHUA, CHEN LI, et al.Enhancement on the afterglow properties of Sr2MgSi2O7: Eu2+ by Er3+ codoping.Materials Letters, 2011, 65(17): 2676-2679.
[7]	YU SHENG-FEI, PI PI-HUI, WEN XIU-FANG et al. Coordination encapsulation on SrAl2O4: Eu2+, Dy3+ phosphor and its characterization.Journal of Inorganic Materials, 2007, 22(4): 642-646.
[8]	PUNG S Y, TAN C H, FAUZI M N A, et al. Luminescence of Sr2MgSi2O7 phosphor prepared by solid state reaction.Advanced Materials Research, 2014, 1024: 344-347.
[9]	SAKAI M, SHIRAISHI S, ZUKAWA T, et al.Phosphor, Light-emitting Device, and Plasma Display Panel. US Patent, 7902756, 2011.3.8.
[10]	SHRIVASTAVA R, KAUR J.Characterisation and mechanoluminescence studies of Sr2MgSi2O7: Eu2+, Dy3+.Journal of Radiation Research and Applied Sciences, 2015, 8(2): 201-207.
[11]	ZHANG Y, WEI W, DAS G K, et al.Engineering lanthanide-based materials for nanomedicine.Journal of Photochemistry and Photobiology C, 2014, 20(9): 71-96.
[12]	POORT S H M, REIJNHOUDT H M, VAN DER KUIP H O T, et al. Luminescence of Eu2+ in silicate host lattices with alkaline earth ions in a row.Journal of Alloys and Compounds, 1996, 241(1/2): 75-81.
[13]	LIN YUANHUA, TANG ZILONG, ZHANG ZHONGTAI, et al.Preparation of a new long afterglow blue-emitting Sr2MgSi2O7- based photoluminescent phosphor.Journal of Materials Science Letters, 2001, 20(16): 1505-1506.
[14]	WU HAOYI, HU YIHUA, WANG YINHAI, et al.Influence on luminescent properties of the Sr2MgSi2O7: Eu2+ by Dy3+, Nd3+ co-doping.Journal of Alloys and Compounds, 2009, 486(1): 549-553.
[15]	ZHANG XINGUO, TANG XUEPING, ZHANG JILIN, et al.Luminescent properties of Sr2MgSi2O7: Eu2+ as blue phosphor for NUV light-emitting diodes.Powder Technology, 2010, 204(2): 263-267.
[16]	ALVANI A A S, MOZTARZADEH F, SARABI A A. Preparation and properties of long afterglow in alkaline earth silicate phosphors co-doped by Eu2O3 and Dy2O3.Journal of Luminescence, 2005, 115(3): 147-150.
[17]	SHI CHAOSHU, FU YIBING, LIU BO, et al. The roles of Eu2+ and Dy3+ in the blue long-lasting phosphor Sr2MgSi2O7: Eu2+, Dy3+. Journal of Luminescence, 2007, 122-123: 11-13.
[18]	SAHU I P, BISEN D P, TAMRAKAR R K, et al.Enhancement of the photoluminescence and long afterglow properties of Sr2MgSi2O7: Eu2+ phosphor by Dy3+ co-doping.Luminescence, 2015, 30(8): 1318-1325.
[19]	WU HAOYI, HU YIHUA, WANG YINHAI, et al.Influence on the luminescence properties of the lattice defects in Sr2MgSi2O7: Eu2+, M (M = Dy3+, La3+ or Na1+).Journal of Alloys and Compounds, 2010, 497(1): 330-335.
[20]	ZHU YANAN, CHEN ZHI, GE MINGQIAO.Preparation of Sr2MgSi2O7: Eu2+, Dy3+ nanofiber by electrospinning assisted solid-state reaction.Journal of Materials Science: Materials in Electronics, 2014, 25(12): 5512-5517.
[21]	DEXTER D L.A theory of sensitized luminescence in solids.Journal of Chemical Physics, 1953, 21(5): 836-850.
[22]	JIANG LING, CHANG CHENGKANG, MAO DALI, et al.Concentration quenching of Eu2+ in Ca2MgSi2O7: Eu2+ phosphor.Materials Science and Engineering B, 2003, 103(3): 271-275.
[23]	BLASSE G, GRABMAIER B C. Luminescent Materials, 1st edition. Berlin: Springer, 1994: 10-32.
[24]	ZHANG MEI, HE XIN, LUO JIANYI, et al.Dependence of optical properties on the composition of (Ba1-x-ySrxEuy)Si2O2N2 phosphors for white light emitting diodes.Materials Chemistry and Physics, 2014, 147(3): 968-973.
[25]	SONG X F, FU R L, AGATHOPOULOS S, et al.Photoluminescence properties of Eu2+-activated CaSi2O2N2: redshift and concentration quenching.Journal of Applied Physics, 2009, 106(3): 033103.
[26]	SONG FENGLAN, CHEN DONGHUA, YUAN YUHONG.Synthesis of Sr2MgSi2O7: Eu, Dy and Sr2MgSi2O7: Eu, Dy, Nd by a modified solid-state reaction and their luminescent properties.Journal of Alloys and Compounds, 2008, 458(1): 564-568.
[27]	ROH H S, CHO I S, AN J S, et al.Enhanced photoluminescence property of Dy3+ co-doped BaAl2O4: Eu2+ green phosphors.Ceramics International, 2012, 38(1): 443-447.
[28]	SHIN H, ULLAH S, CHUNG K.Effect of nominal substitution of Dy3+ for host cations in SrAl2O4: Eu2+ phosphor on phase evolution and long afterglow luminescence.Journal of Alloys and Compounds, 2012, 544: 181-187.
[29]	HARANATH D, SHARMA P, CHANDER H.Optimization of boric acid content in developing efficient blue emitting, long persistent phosphor.Journal of Physics D, 2005, 38(3): 371-375.
[30]	GUPTA B K, KUMAR A, KUMAR P, et al.Probing on green long persistent Eu2+/Dy3+ doped Sr3SiAl4O11 emerging phosphor for security applications.Journal of Applied Physics, 2015, 117(24): 243104.
[31]	JU GIUFANG, HU YIHUA, CHEN LI, et al.Concentration quenching of persistent luminescence.Physica B, 2013, 415: 1-4.

Influence of Eu²⁺ and Dy³⁺ Concentrations on Fluorescence and Phosphorescence of Sr₂MgSi₂O₇ Phosphors

RichHTML

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

Figures/Tables 12

References 31

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	SHEN Hao, CHEN Qianqian, ZHOU Boxiang, TANG Xiaodong, ZHANG Yuanyuan. Preparation and Energy Storage Properties of A-site La/Sr Co-doped PbZrO₃ Thin Films [J]. Journal of Inorganic Materials, 2024, 39(9): 1022-1028.
[2]	CHENG Jun, ZHANG Jiawei, QIU Pengfei, CHEN Lidong, SHI Xun. Preparation and Thermoelectric Transport Properties of P-doped β-FeSi₂ [J]. Journal of Inorganic Materials, 2024, 39(8): 895-902.
[3]	ZHAO Zhihan, GUO Peng, WEI Jing, CUI Li, LIU Shanze, ZHANG Wenlong, CHEN Rende, WANG Aiying. Ti Doped Diamond Like Carbon Films: Piezoresistive Properties and Carrier Transport Behavior [J]. Journal of Inorganic Materials, 2024, 39(8): 879-886.
[4]	LI Jiaqi, LI Xiaosong, LI Xuanhe, ZHU Xiaobing, ZHU Aimin. Transition Metal-doped Manganese Oxide: Synthesis by Warm Plasma and Electrocatalytic Performance for Oxygen Evolution Reaction [J]. Journal of Inorganic Materials, 2024, 39(7): 835-844.
[5]	TAM YU Puy Mang, XU Yu, GAO Quanhao, ZHOU Haiqiong, ZHANG Zhen, YIN Hao, LI Zhen, LÜ Qitao, CHEN Zhenqiang, MA Fengkai, SU Liangbi. Spectroscopic Properties and Optical Clusters in Erbium-doped CaF₂, SrF₂ and PbF₂ Crystals [J]. Journal of Inorganic Materials, 2024, 39(3): 330-336.
[6]	LI Qiushi, YIN Guangming, LÜ Weichao, WANG Huaiyao, LI Jinglin, YANG Hongguang, GUAN Fangfang. Preparation of Na⁺/g-C₃N₄ Materials and Their Photocatalytic Degradation Mechanism on Methylene Blue [J]. Journal of Inorganic Materials, 2024, 39(10): 1143-1150.
[7]	DAI Le, LIU Yang, GAO Xuan, WANG Shuhao, SONG Yating, TANG Mingmeng, DMITRY V Karpinsky, LIU Lisha, WANG Yaojin. Self-polarization Achieved by Compositionally Gradient Doping in BiFeO₃ Thin Films [J]. Journal of Inorganic Materials, 2024, 39(1): 99-106.
[8]	LI Guanglan, WANG Tianyu, LIU Yichen, LU Zhongfa. Layered NiFeCo-LDH-Ti₆C_3.75 Catalyst: Preparation and Performance for Oxygen Evolution Reaction [J]. Journal of Inorganic Materials, 2023, 38(7): 823-829.
[9]	KONG Guoqiang, LENG Mingzhe, ZHOU Zhanrong, XIA Chi, SHEN Xiaofang. Sb Doped O3 Type Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂ Cathode Material for Na-ion Battery [J]. Journal of Inorganic Materials, 2023, 38(6): 656-662.
[10]	YANG Yingkang, SHAO Yiqing, LI Bailiang, LÜ Zhiwei, WANG Lulu, WANG Liangjun, CAO Xun, WU Yuning, HUANG Rong, YANG Chang. Enhanced Band-edge Luminescence of CuI Thin Film by Cl-doping [J]. Journal of Inorganic Materials, 2023, 38(6): 687-692.
[11]	QI Zhanguo, LIU Lei, WANG Shouzhi, WANG Guogong, YU Jiaoxian, WANG Zhongxin, DUAN Xiulan, XU Xiangang, ZHANG Lei. Progress in GaN Single Crystals: HVPE Growth and Doping [J]. Journal of Inorganic Materials, 2023, 38(3): 243-255.
[12]	WANG Zhiqiang, WU Ji’an, CHEN Kunfeng, XUE Dongfeng. Large-size Er,Yb:YAG Single Crystal: Growth and Performance [J]. Journal of Inorganic Materials, 2023, 38(3): 329-334.
[13]	LI Jianbo, TIAN Zhen, JIANG Quanwei, YU Lifeng, KANG Huijun, CAO Zhiqiang, WANG Tongmin. Effects of Different Element Doping on Microstructure and Thermoelectric Properties of CaTiO₃ [J]. Journal of Inorganic Materials, 2023, 38(12): 1396-1404.
[14]	LU Chenhui, GE Wanyin, SONG Panpan, ZHANG Panfeng, XU Meimei, ZHANG Wei. Luminescence Property of Eu Doped SiAlON Phosphors for White LEDs [J]. Journal of Inorganic Materials, 2023, 38(1): 97-104.
[15]	WANG Yang, FAN Guangxin, LIU Pei, YIN Jinpei, LIU Baozhong, ZHU Linjian, LUO Chengguo. Microscopic Mechanism of K⁺ Doping on Performance of Lithium Manganese Cathode for Li-ion Battery [J]. Journal of Inorganic Materials, 2022, 37(9): 1023-1029.