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

doi:10.15541/jim20220504

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 11

References 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]

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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