980 nm LD泵浦下Dy3+/Yb3+共掺碲酸盐玻璃3 μm波段中红外宽带发光特性

doi:10.15541/jim20240441

摘要/Abstract

摘要：

3~5 μm中红外激光在大气通信、环境监测、医疗、国防等领域有着广泛的应用。本研究采用熔融-淬冷法在惰性气氛保护手套箱中制备了Dy³⁺、Yb³⁺单掺和Dy³⁺/Yb³⁺共掺70TeO₂-25ZnO-5La₂O₃系列玻璃样品, 通过差示扫描量热(DSC)法、X射线衍射(XRD)、拉曼光谱、透过光谱以及3 μm波段荧光光谱等测试方法对玻璃的热学和结构特性、羟基含量和中红外发光性能进行了表征。其中, 70TeO₂-25ZnO-5La₂O₃玻璃具有较高的抗析晶稳定性(ΔT=101 ℃)、较低的声子能量(760 cm^-1)。980 nm激光二极管(LD)泵浦下Dy³⁺/Yb³⁺共掺碲酸盐玻璃产生了3 μm波段宽带荧光发射, 荧光半高宽(FWHM)为326 nm。这主要归因于Yb³⁺→Dy³⁺能量传递效率高(98.74%)和3 μm附近较低的羟基吸收系数(0.32 cm^-1)。根据Judd-Ofelt和Dexter理论计算了Dy³⁺离子的自发辐射跃迁概率、荧光分支比等光谱参数, 以及Yb³⁺→Dy³⁺能量传递微观参数, 讨论并确定了Yb³⁺: ²F_5/2→Dy³⁺: ⁶H_7/2, ⁶F_9/2为主要的能量传递通道。研究表明, 低羟基Dy³⁺/Yb³⁺共掺TeO₂-ZnO-La₂O₃玻璃可以作为优良的3 μm中红外增益介质。

关键词: 中红外, Dy³⁺/Yb³⁺共掺, Judd-Ofelt理论, Dexter理论, 能量传递微观参数

Abstract:

Three to five μm mid-infrared laser has broad applications in atmospheric communication, environmental monitoring, medical treatment, and defense. Here, a series of glasses with compositions of 70TeO₂-25ZnO-5La₂O₃, doped with Dy³⁺ or Yb³⁺, and co-doped with Dy³⁺/Yb³⁺, were prepared using the melt-quenching method in an inert atmosphere-protected glovebox. Thermal properties, structural characteristics, hydroxyl content, and mid-infrared luminescence of the glasses were characterized through measurements such as differential scanning calorimetry (DSC), X-ray diffraction (XRD), Raman spectra, transmission spectra, and 3 μm band fluorescence spectra. The results indicate that 70TeO₂-25ZnO-5La₂O₃ glass possesses high resistance to crystallization (ΔT=101 ℃) and low phonon energy (760 cm^-1). Under 980 nm laser diode (LD) excitation, Dy³⁺/Yb³⁺ co-doped tellurite glass produces a broadband fluorescence emission around 3 μm region, with a full width at half maximum (FWHM) of 326 nm. This is attributed to the high energy transfer efficiency from Yb³⁺ to Dy³⁺ (98.74%) and the low hydroxyl absorption coefficient near 3 μm (0.32 cm^-1). Based on Judd-Ofelt and Dexter theories, spontaneous radiative transition probability, fluorescence branching ratio, and other spectroscopic parameters of Dy³⁺ ions, as well as microscopic parameters of Yb³⁺→Dy³⁺ energy transfer, were calculated. The primary energy transfer pathway is analyzed and identified as Yb³⁺: ²F_5/2→Dy³⁺: ⁶H_7/2, ⁶F_9/2. This study demonstrates that the low-hydroxyl Dy³⁺/Yb³⁺ co-doped TeO₂-ZnO-La₂O₃ glass can serve as an excellent 3 μm mid-infrared gain medium.

Key words: mid-infrared, Dy³⁺/Yb³⁺ co-doping, Judd-Ofelt theory, Dexter theory, energy transfer microparameter

中图分类号:

TQ171

潘雨舟, 何法鉴, 徐路路, 戴世勋. 980 nm LD泵浦下Dy³⁺/Yb³⁺共掺碲酸盐玻璃3 μm波段中红外宽带发光特性[J]. 无机材料学报, 2025, 40(5): 521-528.

PAN Yuzhou, HE Fajian, XU Lulu, DAI Shixun. Broadband 3 μm Mid-infrared Emission in Dy³⁺/Yb³⁺ Co-doped Tellurite Glass under 980 nm LD Excitation[J]. Journal of Inorganic Materials, 2025, 40(5): 521-528.

图/表 15

图1 TZL样品的DSC曲线

Fig. 1 DSC curve of TZL sample

图2 TZL样品的XRD谱图

Fig. 2 XRD pattern of TZL sample

表1 TZL-Dy/Yb样品的标称含量和实际含量

Table 1 Nominal and actual composition of TZL-Dy/Yb sample

Component element	Mass percentage/%	Test percentage/%
Te	70.80	70
Zn	12.80	13
La	11.00	11
Dy	2.64	3
Yb	2.76	3

图3 TZL-Dy/Yb样品中(a) Dy3+和(b) Yb3+离子分布

Fig. 3 Distribution of (a) Dy3+ and (b) Yb3+ ions in TZL-Dy/Yb sample

图4 TZL样品的拉曼光谱图

Fig. 4 Raman spectrum of TZL sample

图5 TZL样品的透过光谱图

Fig. 5 Transmission spectrum of TZL sample

图6 全部样品的吸收光谱图(a)及Dy3+和Yb3+离子间能级图(b)

Fig. 6 Absorption spectra of all samples (a) and energy level diagram of Dy3+ and Yb3+ ions (b)

表2 不同掺Dy3+玻璃的J-O强度参数Ωt(t=2、4、6)

Table 2 J-O intensities, parameters Ωt (t=2, 4, 6) of Dy3+ in various glasses

Glass	Ω_t/(×10^-20, cm²)			Ω₄/Ω₆	Ref.
Glass	Ω₂	Ω₄	Ω₆	Ω₄/Ω₆	Ref.
80(0.8GeS₂·0.2Ga₂S₃)·20CdI₂	14.26	1.10	2.73	0.40	[21]
ZBLAY	3.16	1.67	2.45	0.68	[9]
LiYF₄ crystal	2.01	1.34	2.39	0.56	[20]
70TeO₂-25ZnO-5La₂O₃	3.54	0.76	1.10	0.69	This work

表3 TZL-Dy样品中Dy3+离子的辐射光谱参数

Table 3 Radiative spectral parameters of Dy3+ ions in TZL-Dy sample

Transition	A/s^-1	β/%	τ/ms
⁶H_13/2→⁶H_15/2	51.44	100	19.44
⁶H_11/2→⁶H_13/2	14.77	12	-
→⁶H_15/2	110.22	88	8.00
⁶H_9/2→⁶H_11/2	6.20	6	-
→⁶H_13/2	31.31	30	-
→⁶H_15/2	65.59	64	9.70

图7 TZL-Dy和TZL-Dy/Yb样品的荧光光谱

Fig. 7 Fluorescence spectra of TZL-Dy and TZL-Dy/Yb samples

图8 各样品中Yb3+: 2F5/2能级和Dy3+: 6H13/2能级的荧光衰减曲线

Fig. 8 Fluorescence decay curves of Yb3+: 2F5/2 level and Dy3+: 6H13/2 level in each sample (a, b) Yb3+: 2F5/2 in (a) TZL-Yb and (b) TZL-Dy/Yb samples; (c, d) Dy3+: 6H13/2 in (c) TZL-Dy and (d) TZL-Dy/Yb samples

图9 TZL-Dy/Yb样品中Dy3+: 6H13/2→6H15/2跃迁的吸收和发射截面

Fig. 9 Absorption and emission cross-sections of Dy3+: 6H13/2→6H15/2 transitions in TZL-Dy/Yb sample

图10 TZL-Dy/Yb样品中Dy3+: 6H13/2→6H15/2跃迁的增益截面

Fig. 10 Gain cross-section of Dy3+: 6H13/2→6H15/2 transition in TZL-Dy/Yb sample

表4 Yb3+离子和Dy3+离子之间能量传递的能量传递微观系数、临界半径、声子数和贡献比

Table 4 Energy transfer micro-coefficient, critical radius, phonon number and contribution ratio in energy transfers between Yb3+ and Dy3+ ions

Energy transfer	Phonon number (N), contribution ratio/%				C_D-A/(×10^-40, cm⁶·s^-1)	R_C/nm
Energy transfer	0	1	2	3	C_D-A/(×10^-40, cm⁶·s^-1)	R_C/nm
ET1 (Yb³⁺: ²F_5/2→Dy³⁺: ⁶F_7/2)	99.92	0.08	0	0	0.82	0.700
ET2 (Yb³⁺: ²F_5/2→Dy³⁺: ⁶H_7/2, ⁶F_9/2)	11.49	85.50	3.01	0	9.36	1.050
ET3 (Yb³⁺: ²F_5/2→Dy³⁺: ⁶H_9/2, ⁶F_11/2)	0	0	55.61	44.39	1.35	0.760

图11 TZL-Dy/Yb样品中Yb3+: 2F5/2→2F7/2发射截面及发射边带与各个Dy3+吸收截面的光谱重叠情况

Fig. 11 Spectral overlap of Yb3+: 2F5/2→2F7/2 emission cross-section, emission sidebands, and various absorption cross-sections of Dy3+ in TZL-Dy/Yb sample (a) Dy3+: 6H15/2→6F7/2; (b) Dy3+: 6H15/2→6H7/2, 6F9/2; (c) Dy3+: 6H15/2→6H9/2, 6F11/2

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980 nm LD泵浦下Dy³⁺/Yb³⁺共掺碲酸盐玻璃3 μm波段中红外宽带发光特性

Broadband 3 μm Mid-infrared Emission in Dy³⁺/Yb³⁺ Co-doped Tellurite Glass under 980 nm LD Excitation

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