Dy3+掺杂SrGdGa3O7晶体的晶体生长, 结构、光学和可见光荧光特性

doi:10.15541/jim20230059

无机材料学报 ›› 2023, Vol. 38 ›› Issue (12): 1475-1482.DOI: 10.15541/jim20230059

所属专题：【信息功能】透明陶瓷与闪烁晶体（202312）

Dy³⁺掺杂SrGdGa₃O₇晶体的晶体生长, 结构、光学和可见光荧光特性

王海东¹^,²^,³(), 王燕¹^,³, 朱昭捷¹^,³, 李坚富¹^,³, LAKSHMINARAYANA Gandham⁴, 涂朝阳¹^,³()

1.中国科学院福建物质结构研究所, 福州 350002
2.中国科学院大学, 北京 100049
3.中国福建光电信息科学与技术创新实验室(闽都创新实验室), 福州 350108
4.韩国庆北国立大学智能建筑自动化中心, 大邱 41566, 韩国

收稿日期:2023-02-06 修回日期:2023-02-27 出版日期:2023-09-12 网络出版日期:2023-09-12
通讯作者: 涂朝阳, 研究员. E-mail: tcy@fjirsm.ac.cn
作者简介:王海东(1997-), 男, 硕士研究生. E-mail: wanghaidong@fjirsm.ac.cn

Crystal Growth and Structural, Optical, and Visible Fluorescence Traits of Dy³⁺-doped SrGdGa₃O₇ Crystal

WANG Haidong¹^,²^,³(), WANG Yan¹^,³, ZHU Zhaojie¹^,³, LI Jianfu¹^,³, LAKSHMINARAYANA Gandham⁴, TU Chaoyang¹^,³()

1. Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China
4. Intelligent Construction Automation Center, Kyungpook National University, Daegu 41566, Republic of Korea

Received:2023-02-06 Revised:2023-02-27 Published:2023-09-12 Online:2023-09-12
Contact: TU Chaoyang, professor. E-mail: tcy@fjirsm.ac.cn
About author:WANG Haidong (1997-), male, Master candidate. E-mail: wanghaidong@fjirsm.ac.cn
Supported by:
National Natural Science Foundation of China(51832007);National Natural Science Foundation of China(51872286);National Key Research and Development Program of China(2022YFB3605704);NSFC-Joint Funds for Regional Innovation and Development(U21A20508);Science and Technology Plan Leading Project of Fujian Province(2022H0043);Science and Technology Plan Leading Project of Fujian Province(2020H0036);Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR204);Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2020zz108);The 14th Five-year Plan Project of FJIRSM(E255KL0101);Science and Technology Service Network Initiative(2019T3006)

摘要/Abstract

摘要：

采用Chzochralski方法成功生长了Dy³⁺掺杂的SrGdGa₃O₇晶体, 并对其结构和光学特性进行了详细研究。基于XRD数据, 采用Rietveld法优化了晶体的晶格参数。分析了Dy: SrGdGa₃O₇晶体的偏振吸收谱、偏振发射谱和荧光衰减曲线。在452 nm处, π偏振和σ偏振对应的吸收截面分别为0.594×10^-21和0.555×10^-21 cm²。计算得到的有效J-O强度参数Ω₂、Ω₄和Ω₆分别为5.495×10^-20、1.476×10^-20和1.110×10^-20 cm²。J-O理论分析和荧光光谱表明: 在452 nm激发下, Dy: SrGdGa₃O₇晶体⁴F_9/2→⁶H_13/2跃迁在可见光波段具有最高的荧光分支比和荧光强度, 在574 nm处的π和σ偏振发射截面分别为1.84×10^-21和2.49×10^-21 cm²。Dy³⁺: ⁴F_9/2能级的辐射寿命和荧光寿命分别为0.768和0.531 ms, 量子效率为69.1%。研究结果表明: Dy³⁺: SrGdGa₃O₇晶体是一种潜在的可用于蓝光LD泵浦实现黄激光的材料。

关键词: 晶体生长, Dy³⁺: SrGdGa₃O₇, 光学性能, 黄光发射

Abstract:

Dy³⁺-doped SrGdGa₃O₇ crystal was successfully grown through the Czochralski method and investigated in detail for its structural and optical features. Its crystallographic lattice parameters were optimized by Rietveld refinement based on XRD data. Polarized absorption spectra, polarized emission spectra, and fluorescence decay curves of Dy: SrGdGa₃O₇ crystal were analyzed. Absorption cross-sections at 452 nm corresponding to π- and σ-polarization were computed as 0.594×10^-21 and 0.555×10^-21 cm², respectively. Calculated effective J-O intensity parameters Ω₂, Ω₄, and Ω₆ were 5.495×10^-20, 1.476×10^-20, and 1.110×10^-20 cm², respectively. J-O analysis and emission spectra show that transition ⁴F_9/2→⁶H_13/2 of Dy: SrGdGa₃O₇ crystal has the highest fluorescence branching ratio and fluorescence intensity under 452 nm excitation within the visible spectral region, the emission cross-sections of π- and σ-polarization were 1.84×10^-21 and 2.49×10^-21 cm² at the wavelength of 574 nm, respectively. The measured radiative lifetime and fluorescence decay time of the Dy³⁺: ⁴F_9/2 level were 0.768 and 0.531 ms with a quantum efficiency of 69.1%. All these results reveal that Dy³⁺: SrGdGa₃O₇ crystal is a promising material for yellow lasers pumped with blue laser diodes.

Key words: crystal growth, Dy³⁺: SrGdGa₃O₇, optical properties, yellow emission

中图分类号:

TN244

王海东, 王燕, 朱昭捷, 李坚富, LAKSHMINARAYANA Gandham, 涂朝阳. Dy³⁺掺杂SrGdGa₃O₇晶体的晶体生长, 结构、光学和可见光荧光特性[J]. 无机材料学报, 2023, 38(12): 1475-1482.

WANG Haidong, WANG Yan, ZHU Zhaojie, LI Jianfu, LAKSHMINARAYANA Gandham, TU Chaoyang. Crystal Growth and Structural, Optical, and Visible Fluorescence Traits of Dy³⁺-doped SrGdGa₃O₇ Crystal[J]. Journal of Inorganic Materials, 2023, 38(12): 1475-1482.

图/表 13

参考文献 40

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Parameter	Dy:SGGM	SGGM (PDF#50-1835)
a, b/nm	0.79741	0.79651
c/nm	0.52599	0.52368
V/nm³	0.334460	0.33224
ρ/(g·cm^-3)	5.670	5.658
Space group	P$\bar{4}$2₁m
R_wp	12.456%
χ²	1.35

Parameter	Dy:SGGM	SGGM (PDF#50-1835)
a, b/nm	0.79741	0.79651
c/nm	0.52599	0.52368
V/nm³	0.334460	0.33224
ρ/(g·cm^-3)	5.670	5.658
Space group	P$\bar{4}$2₁m
R_wp	12.456%
χ²	1.35

Crystal	λ/nm	FWHM/ nm	σ_abs/ (×10^-21, cm²)	Ref.
Dy: CeF₃	450	9.4	0.61	[20]
Dy: PbWO₄	454	5.71	1.42	[26]
Dy: CNGS	453	10.2	1.2	[27]
Dy: Sr₃Y(BO₃)₃	450	8(π) 10(σ)	0.8(π) 0.6(σ)	[28]
Dy: CaYAlO₄	453	-	3.3(π) 2.1(σ)	[21]
Dy: CaGdAlO₄	452	2.5(π) 4.3(σ)	1.28(π) 2.43(σ)	[22]
Dy: YAG	447	1.9	2.3	[23]
Dy: SGGM	452	10.4(π) 11.8(σ)	0.594(π) 0.555(σ)	This work

Crystal	λ/nm	FWHM/ nm	σ_abs/ (×10^-21, cm²)	Ref.
Dy: CeF₃	450	9.4	0.61	[20]
Dy: PbWO₄	454	5.71	1.42	[26]
Dy: CNGS	453	10.2	1.2	[27]
Dy: Sr₃Y(BO₃)₃	450	8(π) 10(σ)	0.8(π) 0.6(σ)	[28]
Dy: CaYAlO₄	453	-	3.3(π) 2.1(σ)	[21]
Dy: CaGdAlO₄	452	2.5(π) 4.3(σ)	1.28(π) 2.43(σ)	[22]
Dy: YAG	447	1.9	2.3	[23]
Dy: SGGM	452	10.4(π) 11.8(σ)	0.594(π) 0.555(σ)	This work

Transition ⁶H_15/2→	π-polarization			σ-polarization
Transition ⁶H_15/2→	$\bar{\lambda}$/nm	S_exp/(×10^-20, cm²)	S_calc/(×10^-20, cm²)	$\bar{\lambda}$/nm	S_exp/(×10^-20, cm²)	S_calc/(×10^-20, cm²)
⁴G_11/2	426	0.053	0.028	422	0.076	0.022
⁴I_15/2	450	0.104	0.093	450	0.148	0.123
⁴F_9/2	470	0.039	0.033	473	0.055	0.043
⁶F_3/2	766	0.088	0.051	761	0.077	0.076
⁶F_5/2	791	0.286	0.291	792	0.403	0.429
⁶F_7/2	893	0.978	0.846	901	1.179	1.067
⁶H_7/2+⁶F_9/2	1074	1.631	1.672	1079	1.677	1.701
⁶H_9/2+⁶F_11/2	1266	6.670	6.660	1259	6.961	6.953
⁶H_11/2	1693	0.970	1.078	1656	1.292	1.370
RMS/(×10^-20, cm²)		0.074			0.063

Dy³⁺掺杂SrGdGa₃O₇晶体的晶体生长, 结构、光学和可见光荧光特性

Crystal Growth and Structural, Optical, and Visible Fluorescence Traits of Dy³⁺-doped SrGdGa₃O₇ Crystal

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Crystal	Ω₂/(×10^-20, cm²)	Ω₄/(×10^-20, cm²)	Ω₆/(×10^-20, cm²)	Ref.
Dy: LiLuF₄	2.04	0.91	1.09	[34]
Dy: YAG	1.49	0.94	3.20	[23]
Dy: CaGdAlO₄	1.80	1.00	0.50	[22]
Dy: CaYAlO₄	5.05	9.95	3.12	[21]
Dy: Sr₃Y(BO₃)₃	2.39	0.88	1.22	[28]
Dy: LiNbO₃	5.42	1.14	2.51	[35]
Dy: YSGG	0.13	0.73	1.06	[36]
Dy: GGG	0.17	2.66	2.57	[31]
Dy: SGGM	5.113 (π) 5.686 (σ) 5.495 (eff)	1.796 (π) 1.316 (σ) 1.476 (eff)	0.843 (π) 1.243 (σ) 1.110 (eff)	This work

Transitions ⁴F_9/2→	$\bar{\lambda}$/nm	A_ed/s^-1	A_md/s^-1	β	τ_r/ms
⁶F_1/2	1364	0.094	0	7.220×10^-5	0.768
⁶F_3/2	1270	0.066	0	5.055×10^-5	-
⁶F_5/2	1157	9.804	0	7.526×10^-3	-
⁶F_7/2	998	4.534	8.413	9.939×10^-3	-
⁶H_5/2	921	3.577	0	2.746×10^-3	-
⁶H_7/2+⁶F_9/2	833	27.488	13.568	0.032	-
⁶H_9/2+⁶F_11/2	756	45.544	81.59	0.098	-
⁶H_11/2	665	86.029	17.474	0.079	-
⁶H_13/2	574	841.755	0	0.646	-
⁶H_15/2	481	162.738	0	0.125	-

Crystals	$\bar{\lambda}$/nm	FWHM/nm	σ_em/(×10^-21, cm²)	τ_r/ms	τ_f/ms	η/%	Ref.
Dy:LiNbO₃	575	-	3.2 (π) 0.3 (σ)	0.292	0.268	91.8	[35]
Dy:YAG	583	-	2.09	1.02	0.4	39.2	[23]
Dy: CaYAlO₄	580	-	2.8 (π) 3.6 (σ)	0.485	0.262	54.0	[21]
Dy:CaGdAlO₄	578	13(π) 14 (σ)	0.55 (π) 0.51 (σ)	0.501	0.222	44.3	[22]
Dy:Sr₃Y(BO₃)₃	576	16 (σ) 17 (π)	1.0 (σ) 1.2 (π)	1.45	0.820	56.6	[28]
Dy: CNGS	572	16.3 (σ) 15.8 (π)	1.35 (σ) 1.89 (π)	1.22	0.293	26.5	[27]
Dy:GGG	581	-	2.62	1.107	0.79	71.4	[31]
Dy:SGGM	574	15.6(π) 16.2(σ)	1.84 (π) 2.49 (σ)	0.768	0.531	69.1	This work

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