0.6%Pr, x%La:CaF2的发光性能研究和Judd-Ofelt分析

doi:10.15541/jim20220504

无机材料学报 ›› 2023, Vol. 38 ›› Issue (3): 357-362.DOI: 10.15541/jim20220504

0.6%Pr, x%La:CaF₂的发光性能研究和Judd-Ofelt分析

钱新宇¹^,²(), 王无敌², 宋青松², 董永军⁴, 薛艳艳², 张晨波², 王庆国², 徐晓东³, 唐慧丽², 曹桂新¹, 徐军²()

1.上海大学材料基因组工程研究院, 上海 200444
2.同济大学高等研究院, 物理科学与工程学院, 先进微结构材料教育部重点实验室, 上海 200092
3.江苏师范大学物理与电子工程学院, 江苏省先进激光材料与器件重点实验室, 徐州 221116
4.南京光宝光电科技有限公司, 南京 210038

收稿日期:2022-08-26 修回日期:2022-10-22 出版日期:2022-12-30 网络出版日期:2022-12-30
通讯作者: 徐军, 教授. E-mail: xujun@mail.shcnc.ac.cn
作者简介:钱新宇(1998-), 男, 硕士研究生. E-mail: 894742295@qq.com

Luminescence Property and Judd-Ofelt Analysis of 0.6%Pr, x%La:CaF₂ Crystals

QIAN Xinyu¹^,²(), WANG Wudi², SONG Qingsong², DONG Yongjun⁴, XUE Yanyan², ZHANG Chenbo², WANG Qingguo², XU Xiaodong³, TANG Huili², CAO Guixin¹, XU Jun²()

1. Materials Genome Institute, Shanghai University, Shanghai 200444, China
2. Key Laboratory of Advanced Micro- Structured Materials of Ministry of Education, School of Physics Science and Engineering, Institute for Advanced Study, Tongji University, Shanghai 200092, China
3. Jiangsu Key Laboratory of Advanced Laser Materials and Devices, School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou 221116, China
4. Nanjing Metalaser Photonics Company Ltd., Nanjing 210038, China

Received:2022-08-26 Revised:2022-10-22 Published:2022-12-30 Online:2022-12-30
Contact: XU Jun, professor. E-mail: xujun@mail.shcnc.ac.cn
About author:QIAN Xinyu (1998-), male, Master candidate. E-mail: 894742295@qq.com
Supported by:
National Natural Science Foundation of China(61621001);National Natural Science Foundation of China(62075166);National Natural Science Foundation of China(61805177);Fundamental Research Funds for the Central Universities(22120210432)

摘要/Abstract

摘要：

氟化钙(CaF₂)是一种良好的激光材料基质, 具有较宽的透过范围(0.125~10 µm)、良好的导热性(9.71 W/(m·K))和低非线性效应系数。在Pr:CaF₂晶体中, [Pr³⁺-Pr³⁺]团簇导致Pr³⁺离子在较低浓度下出现荧光猝灭现象。在CaF₂中共掺入La³⁺离子有可能打破[Pr³⁺-Pr³⁺]团簇。本研究通过温度梯度法(Temperature Gradient Technique, TGT), 成功地生长了一系列共掺入不同浓度La³⁺离子的Pr:CaF₂晶体。在室温下采用X射线粉末衍射、吸收光谱、荧光光谱和荧光衰减寿命对Pr, La:CaF₂晶体进行表征。Pr:CaF₂晶体共掺入La³⁺离子后仍具有立方晶体结构。³P₀→³H₆(604 nm)和³P₀→³F₂(640 nm)处的最大受激发射截面分别为1.36×10^-20和3.18×10^-20 cm², 半峰宽分别为17.0和 3.8 nm。随着La³⁺离子掺杂含量的增加, ³P₀→³H₆(604 nm)处的半峰宽从15.84增加到18.53 nm。0.6%Pr,10%La:CaF₂(原子分数)的最大荧光寿命和光谱质量因子分别为45.82 μs和145.8×10^-20 cm²·μs。上述结果表明: [Pr³⁺-Pr³⁺]离子淬灭团被打破, Pr, La:CaF₂晶体是潜在的激光增益材料, 可应用于橙红色激光领域。

关键词: Pr, La:CaF₂, 光谱性能, Judd-Ofelt理论, 荧光寿命

Abstract:

Calcium fluoride (CaF₂) is an attractive laser material due to its broad transmission range (0.125-10 µm), good thermal conductivity (9.71 W/(m·K)) and low coefficient of nonlinear effect. In Pr:CaF₂ crystal, the [Pr³⁺-Pr³⁺] cluster lead to fluorescence quenching at lower concentrations of Pr³⁺ ions. Therefore, co-doping of La ions in CaF₂ to break the [Pr³⁺-Pr³⁺] cluster deserves further exploration. In this work, a series of Pr:CaF₂ single crystals co-doped with different concertation of La³⁺ ions were successfully grown by temperature gradient technique (TGT). The X-ray powder diffraction, absorption spectra, fluorescence spectra and fluorescence decay lifetime of Pr,La:CaF₂ crystals were measured. Obtained data demonstrated that the Pr:CaF₂ crystals still had the cubic crystal structure after co-doped with La³⁺ ions. The largest stimulated emission cross-sections of ³P₀→³H₆ (604 nm) and ³P₀→³F₂ (640 nm) transitions were calculated to be 1.36×10^-20 cm² and 3.18×10^-20 cm² with FWHM of 17.0 nm and 3.8 nm, respectively. With the increase of La³⁺ ion concentration, the value of FWHM increased from 15.84 nm to 18.53 nm of ³P₀→³H₆. The largest fluorescent lifetime and spectral quality factor of 0.6%Pr, 10%La:CaF₂ (atom fraction) is 45.82 μs and 1.458×10^-18 cm²·μs, respectively. All above results show that the [Pr³⁺-Pr³⁺] ions quench clusters are broken by La³⁺ ions. The Pr, La:CaF₂ crystal is a potential laser gain material for orange-red laser operation.

Key words: Pr, La:CaF₂, spectra property, Judd-Ofelt theory, fluorescence lifetime

中图分类号:

TQ174

钱新宇, 王无敌, 宋青松, 董永军, 薛艳艳, 张晨波, 王庆国, 徐晓东, 唐慧丽, 曹桂新, 徐军. 0.6%Pr, x%La:CaF₂的发光性能研究和Judd-Ofelt分析[J]. 无机材料学报, 2023, 38(3): 357-362.

QIAN Xinyu, WANG Wudi, SONG Qingsong, DONG Yongjun, XUE Yanyan, ZHANG Chenbo, WANG Qingguo, XU Xiaodong, TANG Huili, CAO Guixin, XU Jun. Luminescence Property and Judd-Ofelt Analysis of 0.6%Pr, x%La:CaF₂ Crystals[J]. Journal of Inorganic Materials, 2023, 38(3): 357-362.

图/表 11

参考文献 33

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Crystal	Initial concentration/%(in atomic)		Actual concentration/%(in atomic)		Segregation coefficient
Crystal	Pr³⁺	La³⁺	Pr³⁺	La³⁺	Pr³⁺	La³⁺
Pr,La:CaF₂	0.60	0.00	0.53	0.00	0.88	-
	0.60	3.00	0.52	3.06	0.86	1.02
	0.60	10.00	0.53	8.59	0.89	0.86
	0.60	18.00	0.47	15.49	0.79	0.86

Crystal	Initial concentration/%(in atomic)		Actual concentration/%(in atomic)		Segregation coefficient
Crystal	Pr³⁺	La³⁺	Pr³⁺	La³⁺	Pr³⁺	La³⁺
Pr,La:CaF₂	0.60	0.00	0.53	0.00	0.88	-
	0.60	3.00	0.52	3.06	0.86	1.02
	0.60	10.00	0.53	8.59	0.89	0.86
	0.60	18.00	0.47	15.49	0.79	0.86

	0.6%Pr,3%La:CaF₂			0.6%Pr,10%La:CaF₂			0.6%Pr,18%La:CaF₂
	λ/nm	S_exp/ (×10^-20, cm²)	S_cal/ (×10^-20, cm²)	λ/nm	S_exp/ (×10^-20, cm²)	S_cal/ (×10^-20, cm²)	λ/nm	S_exp/ (×10^-20, cm²)	S_cal/ (×10^-20, cm²)
³P₂	443	1.848	0.267	443	1.617	0.209	443	2.024	0.269
³P₁+¹I₆	468	0.367	0.214	468	0.376	0.238	468	0.451	0.240
³P₀	483	0.145	0.130	483	0.119	0.150	482	0.240	0.150
¹D₂	591	0.526	0.136	590	0.580	0.111	590	0.461	0.138
¹G₄	1011	0.194	0.027	997	0.205	0.024	991	0.140	0.028
³F₄	1443	0.699	1.011	1442	0.714	0.788	1437	0.820	1.016
³F₃	1550	2.291	1.657	1554	1.727	1.420	1551	2.300	1.706
³F₂	1945	1.161	0.834	1920	1.528	1.377	1936	1.380	1.021
³H₆	2250	0.406	0.296	2252	0.391	0.230	2257	0.334	0.298
RMS ΔS/(×10^-20, cm²)	0.744			0.290			0.793

	0.6%Pr,3%La:CaF₂			0.6%Pr,10%La:CaF₂			0.6%Pr,18%La:CaF₂
	λ/nm	S_exp/ (×10^-20, cm²)	S_cal/ (×10^-20, cm²)	λ/nm	S_exp/ (×10^-20, cm²)	S_cal/ (×10^-20, cm²)	λ/nm	S_exp/ (×10^-20, cm²)	S_cal/ (×10^-20, cm²)
³P₂	443	1.848	0.267	443	1.617	0.209	443	2.024	0.269
³P₁+¹I₆	468	0.367	0.214	468	0.376	0.238	468	0.451	0.240
³P₀	483	0.145	0.130	483	0.119	0.150	482	0.240	0.150
¹D₂	591	0.526	0.136	590	0.580	0.111	590	0.461	0.138
¹G₄	1011	0.194	0.027	997	0.205	0.024	991	0.140	0.028
³F₄	1443	0.699	1.011	1442	0.714	0.788	1437	0.820	1.016
³F₃	1550	2.291	1.657	1554	1.727	1.420	1551	2.300	1.706
³F₂	1945	1.161	0.834	1920	1.528	1.377	1936	1.380	1.021
³H₆	2250	0.406	0.296	2252	0.391	0.230	2257	0.334	0.298
RMS ΔS/(×10^-20, cm²)	0.744			0.290			0.793

Crystal	Ω₂/(×10^-20, cm²)	Ω₄/(×10^-20, cm²)	Ω₆/(×10^-20, cm²)	Ω₄/Ω₆	Ref.
0.6%Pr,3%La:CaF₂	0.59	0.76	1.94	0.39	This work
0.6%Pr,10%La:CaF₂	1.68	0.88	1.44	0.61
0.6%Pr,18%La:CaF₂	0.87	0.87	1.93	0.45
LaF₃	0.72	0.39	4.79	0.08	[22]
CaF₂	1.15	3.60	10.00	0.36	[23]
LYF₄	3.45	3.94	6.13	0.64	[22]
BaY₂F₈	1.09	3.49	2.22	1.57	[23]
KYF₄	3.92	1.78	7.94	0.22	[23]
CaYAlO₄	5.67	8.09	14.90	0.54	[26]
YAlO₃	2.28	3.88	5.15	0.75	[30]
Y₃Al₅O₁₂	0.00	12.20	8.17	1.49	[24]
SrAl₁₁O₁₉	0.84	2.19	6.86	0.32	[30]

0.6%Pr, x%La:CaF₂的发光性能研究和Judd-Ofelt分析

Luminescence Property and Judd-Ofelt Analysis of 0.6%Pr, x%La:CaF₂ Crystals

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Crystal	Transitions from ³P₀	λ/nm	A_ed/S^-1	β/%	τ/μs
0.6%Pr:CaF₂	³H₄	485	2068.02	28.39	137.3
	³H₅	532	0.00	0.00
	³H₆	607	745.80	10.24
	³F₂	645	4081.31	56.04
	³F₃+³F₄	724	387.93	5.33
0.6%Pr,3%La:CaF₂	³H₄	485	2161.59	43.48	201.1
	³H₅	532	0.00	0.00
	³H₆	608	1186.02	23.85
	³F₂	644	1220.94	24.56
	³F₃+³F₄	725	403.47	8.11
0.6%Pr,10%La:CaF₂	³H₄	485	8357.08	34.01	136.3
	³H₅	532	0.00	0.00
	³H₆	608	3557.05	11.95
	³F₂	644	4803.69	47.68
	³F₃+³F₄	725	1562.94	6.36
0.6%Pr,18%La:CaF₂	³H₄	485	559.00	41.82	168.9
	³H₅	532	0.00	0.00
	³H₆	608	3642.46	19.80
	³F₂	644	769.30	30.55
	³F₃+³F₄	725	104.56	7.82

Concentration of La³⁺ ion	Transition	λ_em/nm	FWHM/nm	σ_em/(×10^-20, cm²)
0.6%Pr:CaF₂	³P₀→³H₄	482	5.20	0.77
	³P₀→³H₅	535	26.68	0.00
	³P₀→³H₆	605	15.84	1.14
	³P₀→³F₂	640	5.13	0.96
	³P₀→³F₃+³F₄	723	4.51	0.59
0.6%Pr,3%La:CaF₂	³P₀→³H₄	484	6.76	1.96
	³P₀→³H₅	537	27.45	0.00
	³P₀→³H₆	599	15.30	1.35
	³P₀→³F₂	640	3.12	1.51
	³P₀→³F₃+³F₄	723	5.21	2.48
0.6%Pr,10%La:CaF₂	³P₀→³H₄	484	8.36	2.52
	³P₀→³H₅	535	26.76	0.00
	³P₀→³H₆	599	16.98	1.36
	³P₀→³F₂	640	3.80	3.18
	³P₀→³F₃+³F₄	723	5.49	3.03
0.6%Pr,18%La:CaF₂	³P₀→³H₄	482	9.57	1.22
	³P₀→³H₅	537	26.25	0.00
	³P₀→³H₆	606	18.53	1.24
	³P₀→³F₂	640	3.80	2.92
	³P₀→³F₃+³F₄	723	7.38	1.40

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