掺铒CaF2、SrF2、PbF2晶体的光谱性能与团簇结构研究

doi:10.15541/jim20230462

无机材料学报 ›› 2024, Vol. 39 ›› Issue (3): 330-336.DOI: 10.15541/jim20230462 CSTR: 32189.14.10.15541/jim20230462

所属专题：【AI4材料】Al4材料(202512)

掺铒CaF₂、SrF₂、PbF₂晶体的光谱性能与团簇结构研究

TAM YU Puy Mang¹^,²(), 徐愉³, 高泉浩¹^,², 周海琼¹^,², 张振⁴, 尹浩¹^,⁵, 李真¹^,²^,⁵(), 吕启涛⁵, 陈振强¹^,²^,⁵, 马凤凯¹^,²(), 苏良碧⁴

1.暨南大学光电工程系, 广东省晶体材料与激光技术工程研究中心, 广州510632
2.广东省光纤传感与通信重点实验室, 广州 510632
3.暨南大学分析测试中心, 广州 510632
4.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 201899
5.广东省工业超短脉冲激光技术重点实验室, 深圳 518055

收稿日期:2023-10-09 修回日期:2023-11-20 出版日期:2024-03-20 网络出版日期:2023-11-28
通讯作者: 李真, 教授. E-mail: ailz268@126.com;
马凤凯, 副教授. E-mail: mafengkai@jnu.edu.cn
作者简介:TAM YU Puy Mang (1997-), 女, 硕士研究生. E-mail: pmtamyu@outlook.com

Spectroscopic Properties and Optical Clusters in Erbium-doped CaF₂, SrF₂ and PbF₂ Crystals

TAM YU Puy Mang¹^,²(), XU Yu³, GAO Quanhao¹^,², ZHOU Haiqiong¹^,², ZHANG Zhen⁴, YIN Hao¹^,⁵, LI Zhen¹^,²^,⁵(), LÜ Qitao⁵, CHEN Zhenqiang¹^,²^,⁵, MA Fengkai¹^,²(), SU Liangbi⁴

1. Guangdong Provincial Engineering Research Center of Crystal and Laser Technology, Department of Optoelectronic Engineering, Jinan University, Guangzhou 510632, China
2. Guangdong Provincial Key Laboratory of Optical Fiber Sensing and Communications, Guangzhou 510632, China
3. Analytical and Testing Center, Jinan University, Guangzhou 510632, China
4. The State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
5. Guangdong Provincial Key Laboratory of Industrial Ultrashort Pulse Laser Technology, Shenzhen 518055, China

Received:2023-10-09 Revised:2023-11-20 Published:2024-03-20 Online:2023-11-28
Contact: LI Zhen, professor. E-mail: ailz268@126.com;
MA Fengkai, associate professor. E-mail: mafengkai@jnu.edu.cn
About author:TAM YU Puy Mang (1997-), female, Master candidate. E-mail: pmtamyu@outlook.com
Supported by:
National Key R&D Program of China(2022YFB3605702);National Natural Science Foundation of China(61925508);National Natural Science Foundation of China(61905289);Key-area Research and Development Program of Guangdong Province(2020B090922006);Guangzhou Science and Technology Project(202201010427);CAS Project for Young Scientists in Basic Research(YSBR-024)

摘要/Abstract

摘要：

3 μm波段中红外激光处于大气传输窗口, 又可以作为基础光源, 是激光技术研究的前沿。目前, 铒离子激活的激光晶体材料是产生3 μm中红外激光的重要途径之一。然而, Er³⁺离子⁴I_11/2激光上能级荧光寿命较短, 下能级⁴I_13/2的寿命较长, 难以实现粒子数反转, 导致自终止现象。为了解决这一难题, 往往需要高浓度掺杂, 通过能量传递降低⁴I_13/2能级的寿命。然而高浓度掺杂又会造成晶体热性能变差, 限制了掺Er³⁺激光晶体效率和功率。三阶铒离子容易在氟化物晶体中形成团簇, 导致稀土离子间距缩短, 即使在低掺杂浓度下稀土离子之间的能量传递作用仍较为显著。同时, 低浓度掺杂还可以减轻激光运转下晶体的热堆积效应。掺铒氟化物晶体已成为一类重要的高功率、高效率中红外激光材料。然而, 掺铒氟化物晶体的光谱性能与铒离子团簇结构之间的相互联系尚不明确, 制约了掺铒氟化物晶体光谱和激光性能的进一步发展。本文采用第一性原理计算模拟了铒离子在CaF₂、SrF₂和PbF₂晶体中的团簇结构。结果显示, 铒离子团簇结构随基质晶体变化逐渐演变。结合模拟计算和实验表征定性揭示了不同晶体离子团簇与光谱性能的联系, 为掺铒氟化物中红外激光晶体材料的调控与设计提供参考。

关键词: 铒, 掺杂, 氟化物晶体, 铒离子团簇, 光谱性能

Abstract:

As a fundamental light source and a good window for atmospheric transmission, the mid-infrared 3 μm lasers have led many promising applications. The rare earth doped crystalline materials, such as erbium doped crystals, are some of the most important routes for generation of the lasers. However, they have an intrinsic shortcoming of self-termination because of their short lifetime of ⁴I_11/2 and longer lifetime of ⁴I_13/2. To eliminate this effect, a high concentration doping method is usually adopted to change the energy transfer process to decrease ⁴I_13/2lifetime. The efficiency and output power of Er³⁺-doped crystals were thus limited due to their degraded thermal properties. Trivalent erbium ions are easily clustering in fluoride crystals. Distances among the ions are short and therefore energy transfer processes could be significantly improved in the crystals even doping with low concentrations. Low doping concentrations could also alleviate the thermal effect in laser operations, which enable the erbium doped fluorides to be promising candidates for high power and high efficiency mid-infrared lasers. However, connection of spectral properties and erbium clusters is unknown. Here, the first principles calculation is utilized to model the erbium ion clusters in CaF₂, SrF₂ and PbF₂ crystals, concerning the absorption and photoluminescence properties. The results reveal that spectral properties and structures of the erbium clusters, evolve gradually with matrix crystals. Relationship between spectral properties and optical erbium clusters is determined qualitatively, which could be used to design new erbium doped mid-infrared lasers.

Key words: erbium, doping, mid-infrared laser crystal, erbium cluster, spectroscopic property

中图分类号:

TAM YU Puy Mang, 徐愉, 高泉浩, 周海琼, 张振, 尹浩, 李真, 吕启涛, 陈振强, 马凤凯, 苏良碧. 掺铒CaF₂、SrF₂、PbF₂晶体的光谱性能与团簇结构研究[J]. 无机材料学报, 2024, 39(3): 330-336.

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.

图/表 11

Fig. 1 Energy level diagram of Er3+ ions

Fig. 2 Absorption spectra of Er3+-doped CaF2, SrF2 and PbF2 crystals (a) 4I15/2→2H11/2; (b) 4I15/2→4I11/2; Colorful figures are available on website

Fig. 3 Selective excited and height normalized emission spectra of 4S3/2→4I15/2 transition in Er3+-doped fluoride (a) CaF2; (b) SrF2; (c) PbF2; Colorful figures are available on website

Fig. 4 Comparison of height normalized emission spectra of Er3+-doped CaF2, SrF2 and PbF2 excited at 522 nm

Fig. 5 Number of Er3+ ions dependent formation energy of the clusters in fluoride (a) CaF2; (b) SrF2; (c) PbF2

Fig. 6 Number of rare earth ions dependent formation energy of the clusters (a) La3+:PbF2; (b) Tb3+:PbF2; (c) Y3+:PbF2

Fig. 7 Effective radius of RE3+ dependent formation energy difference, Δμ between 11|0|0|11 and 11|0|0|12 center, RE3+ includes La3+ -Lu3+ and Y3+

Table S1 Formation energy of Er3+ clusters in CaF2, SrF2 and PbF2

Symbol	Formation energy/eV
Symbol	CaF₂	SrF₂	PbF₂
1₁\|0\|0\|1₁	-0.637	-	-
1₁\|0\|0\|1₂	-0.624	-0.725	-0.371
1₁\|0\|1\|2₁	-1.272	-	-
1₁\|0\|4\|2₁	-	-	-1.109
2₁\|0\|2\|2₁	-2.305	-1.700	-1.145^*
2₁\|0\|3\|3₁	-3.214	-2.308	-
2₁\|0\|6\|3₁	-	-	-1.825
3₁\|0\|1\|3₁	-3.909	-2.722^*	-1.662^*
3₁\|0\|5\|4₁	-4.729	-	-
3₁\|0\|8\|4₁	-4.555	-4.200	-3.350
3₁\|0\|8\|4₁-C	-4.628	-4.220	-
4₁\|1\|0\|4₁	-4.328^*	-2.865^*	-1.511^*
4₁\|0\|8\|4₁-O	-5.749	-5.651	-3.754
4₁\|0\|8\|4₁-A1	-5.781	-5.655	-3.807
4₁\|0\|8\|5₁-O	-6.407	-	-
4₁\|0\|8\|5₁-A	-6.564	-	-4.280
5₁\|0\|8\|5₁	-7.860	-7.233	-4.760
6₁\|0\|8\|5₁	-8.568	-8.134	-5.360
6₁\|0\|8\|6₁	-9.042	-	-

Table S2 Formation energy of the clusters in La3+:PbF2, Tb3+:PbF2 and Y3+:PbF2

Symbol	Formation energy/eV
Symbol	La³⁺	Tb³⁺	Y³⁺
1₁\|0\|0\|1₁	-0.107	-	-
1₁\|0\|0\|1₂	-0.204	-0.346	-0.355
1₁\|0\|1\|2₁	-0.653	-0.791	-
1₁\|0\|2\|2₁	-	-	-0.785
2₁\|0\|1\|2₁	-0.914	-	-
2₁\|0\|2\|2₁	-	-1.040	-1.123
2₁\|0\|5\|3₁	-	-1.530	-1.523
2₁\|0\|1\|3₁	-1.580	-	-
3₁\|0\|1\|3₁	-1.911	-1.622^*	-1.590^*
3₁\|0\|2\|4₁	-2.215	-	-
3₁\|0\|8\|4₁	-1.511^*	-3.172	-3.203
4₁\|1\|0\|4₁	-2.319	-1.690^*	-1.488^*
4₁\|0\|8\|4₁-O	-	-3.452	-3.542
4₁\|0\|8\|4₁-A1	-	-3.504	-3.575
4₁\|0\|8\|4₁-A2	-2.132^*	-3.383	-3.417
4₁\|0\|8\|5₁-A	-2.605	-3.984	-4.108
5₁\|0\|8\|5₁	-3.196	-4.585	-4.627
6₁\|0\|8\|5₁	-3.811	-5.153	-5.169
6₁\|0\|8\|6₁	-4.075	-	-

Fig. S1 Salculated thermodynamic stable centers of Er3+ in fluoride (C) CaF2; (S) SrF2; (P) PbF2 Centers are divided into three groups, the monomers, cubic sublattice clusters and square antiprism structure clusters which are denoted as “1”, “2” and “3”, respectively

Fig. S2 Calculated thermodynamic stable centers in PbF2 (La) La3+; (Tb) Tb3+; (Y) Y3+

参考文献 33

[1]	XUE Y Y, XU X D, SU L B, et al. Research progress of mid-infrared laser crystals. Journal of Synthetic Crystals, 2020, 49(8): 1347.
[2]	YANG J, ZHAO J B, LIU Y Y, et al. Near-infrared spectra and laser parameters of Yb³⁺ and Na⁺ codoped CaF₂-SrF₂ crystal. Chinese Journal of Luminescence, 2022, 43(3): 341. DOI URL
[3]	YU T, ZHENG C Z, ZHAO S S, et al. Progress on application of Monte Carlo simulation in studying energy transfer mechanisms for rare-earth luminescent materials. Chinese Journal of Luminescence, 2022, 43(9): 1390. DOI URL
[4]	DINERMAN B J, MOULTON P F. 3-µm CW laser operations in erbium-doped YSGG, GGG, and YAG. Optics Letters, 1994, 19: 1143. DOI URL
[5]	KINTZ G J, ALLEN R, ESTEROWITZ L. CW and pulsed 2.8 μm laser emission from diode-pumped Er³⁺:LiYF₄ at room temperature. Applied Physics Letters, 1987, 50: 1553. DOI URL
[6]	MA F K, ZHANG Z, JIANG D P, et al. Cluster structure of rare earth doped fluorite halide crystals. Journal of Synthetic Crystals, 2023, 52(7): 1219.
[7]	ZHANG M, WANG G J, LIANG Y Y, et al. Continuous-wave laser properties of Er:Lu₂O₃ crystal grown by EFG method. Chinese Journal of Luminescence, 2023, 44(2): 240. DOI URL
[8]	WU X, ZHANG Z, ZHANG Z H, et al. Laser-heated pedestal growth method and characterization of Er:YAP single crystal fibers. Journal of Synthetic Crystals, 2023, 52(7): 1308.
[9]	DONG K P, SUN D L, ZHANG H L, et al. Spectroscopy and LD end-pumped high power 2.79 μm CW laser from an Er:LuYSGG mixed crystal. Journal of Luminescence, 2021, 236(4): 118107. DOI URL
[10]	YANG R, CHEN H R, TU L P, et al. Back energy transfer enhances Er³⁺upconversion luminescence. Chinese Journal of Luminescence, 2023, 44(9): 1552.
[11]	MA F K, SU F, ZHOU R F, et al. The defect aggregation of RE³⁺(RE = Y, La-Lu) in MF₂ (M = Ca, Sr, Ba) fluorites. Materials Research Bulletin, 2020, 125(5): 110788. DOI URL
[12]	QIAN X Y, WANG W D, SONG Q S, et al. Luminescence property and Judd-Ofelt analysis of 0.6%Pr, x%La:CaF₂ crystals. Journal of Inorganic Materials, 2023, 38(3): 357. DOI URL
[13]	ZHANG Z, MA F K, GUO X S, et al. Mid-infrared spectral properties and laser performance of Er³⁺ doped Ca_xSr_1-_xF₂ single crystals. Optical Materials Express, 2018, 8(12): 3820. DOI URL
[14]	WANG H J, KOU H M, WANG Y Z, et al. Irradiation damage of CaF₂ with different yttrium concentrations under 193 nm laser. Journal of Inorganic Materials, 2023, 38(2): 219. DOI URL
[15]	ZHAO X, LIU Z, LIN H, et al. Temperature sensing characteristics of Y₇O₆F₉:Er, Yb/PAN composite fibers based on up-conversion luminescence. Chinese Journal of Luminescence, 2023, 44(2): 279. DOI URL
[16]	LIU J J, FENG X Y, FAN X W, et al. Efficient continuous-wave and passive Q-switched mode-locked Er³⁺:CaF₂-SrF₂ lasers in the mid-infrared region. Optics Letters, 2018, 43(10): 2418. DOI URL
[17]	ZONG M Y, ZHANG Z, LIU J J, et al. LD pumped high-power mid-infrared solid state lasers based on 1.3at%Er³⁺:CaF₂ crystal. Infrared and Laser Engineering, 2021, 50: 20210336. DOI URL
[18]	ZHANG Z, WU Q H, WANG Y X, et al. Efficient 2.76 μm continuous-wave laser in extremely lightly Er-doped CaF₂ single- crystal fiber. Laser Physics Letters, 2020, 17(8): 085801. DOI URL
[19]	ŠVEJKAR R, ŠULC J, JELÍNKOVÁ H, et al. Diode-pumped Er:SrF₂ laser tunable at 2.7 μm. Optical Materials Express, 2018, 8: 1025. DOI URL
[20]	WU G D, YIN X Q, FAN M D, et al. Nd-doped structurally disordered YSr₃(PO₄)₃ single crystal: growth and laser performances. Journal of Rare Earths, 2021, 39(12): 1540. DOI URL
[21]	KRESSE G, FURTHMÜLLER J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 1996, 6: 15. DOI URL
[22]	PERDEW J, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77: 3865. DOI PMID
[23]	BLÖCHL P. Projector augmented-wave method. Physical Review B, 1994, 50: 17953. DOI PMID
[24]	MA F K, ZHOU H Q, TANG Q Y, et al. Clusters modification for tunable photoluminescence in Nd³⁺:SrF₂ crystal. Journal of Alloys and Compounds, 2022, 899: 162913. DOI URL
[25]	KOLOBKOVA E, NIKONOROV N, BABKINA A, et al. Concentration dependence of upconversion luminescence of Er³⁺/Yb³⁺in the fluorophosphate glasses with small phosphates content. Optical Materials, 2020, 109(8): 110279. DOI URL
[26]	TORQUATO A, OLIVEIRAS R A, SALES T O, et al. Influence of PbF₂ content on optical thermometry of Er³⁺/Yb³⁺co-doped tungsten sodium phosphate glasses. Optical Materials, 2021, 112(12): 110723. DOI URL
[27]	CORISH J, CATLOW C R A, JACOBS P W M, et al. Defect aggregation in anion-excess fluorites. Dopant monomers and dimers. Physical Review B, 1982, 25: 6425. DOI URL
[28]	BENDALL P J, CATLOW C R A, CORISH J, et al. Defect aggregation in anion-excess fluorites II. Clusters containing more than two impurity atoms. Journal of Solid State Chemistry, 1984, 51: 159. DOI URL
[29]	KAMINSKII A, ZHMUROVA Z, LOMONOV V, et al. Two stimulated emission ⁴F_3/2→⁴I_11/2, _13/2 channels of Nd³⁺ ions in crystals of the CaF₂-ScF₃ system. Physica Status Solidi A, 1984, 84: K81. DOI URL
[30]	TALLANT D R, WRIGHT J C. Selective laser excitation of charge compensated sites in CaF₂:Er³⁺. Journal of Chemical Physics, 1975, 63: 2074.
[31]	MA F K, ZHANG Z, JIANG D P, et al. Neodymium cluster evolution in fluorite laser crystal: a combined DFT and synchrotron X-ray absorption fine structure study. Crystal Growth & Design, 2022, 22: 4480. DOI URL
[32]	MA F K, ZHANG P X, SU L B, et al. The host driven local structures modulation towards broadband photoluminescence in neodymium-doped fluorite crystal. Optical Materials, 2021, 119(9): 111322. DOI URL
[33]	CAI J J, MA C G, YIN M. Factors influencing the structure of the complex-defects in AF₂: RE³⁺ (A=Ca, Sr and Ba): a first-principles study. Journal of Luminescence, 2022, 250(6): 119058. DOI URL

掺铒CaF₂、SrF₂、PbF₂晶体的光谱性能与团簇结构研究

Spectroscopic Properties and Optical Clusters in Erbium-doped CaF₂, SrF₂ and PbF₂ Crystals

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 33

相关文章 15

编辑推荐

Metrics

本文评价

[1]	汪加辉, 刘晶晶, 邱毅, 王永霞, 崔香枝. 原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能[J]. 无机材料学报, 2026, 41(6): 814-822.
[2]	钱新宇, 王无敌, 郭俊尧, 任永春, 董建树, 王庆国, 唐慧丽, 张晨波, 徐晓东, 董永军, 华伟, 徐军. Ho:BaF₂晶体在近红外-中红外波段光谱性能分析[J]. 无机材料学报, 2026, 41(5): 595-603.
[3]	秦英, 姚焯, 郑丽君, 包硕, 李鹏, 郭诗淇. 柔性超级电容器硫掺杂石墨烯/导电聚合物复合电极材料的制备及性能研究[J]. 无机材料学报, 2026, 41(5): 604-610.
[4]	马晓佳, 耿欣宇, 张卫珂. 硼氮共掺杂生物质碳球负极材料的制备及其储钠性能[J]. 无机材料学报, 2026, 41(4): 469-478.
[5]	徐浩, 顾海涛, 吴鸿辉, 岳晓飞, 林思琪, 金敏. Bi掺杂InSe晶体生长及性能研究[J]. 无机材料学报, 2026, 41(4): 493-499.
[6]	陈坤, 姜勇刚, 冯军宗, 李良军, 胡艺洁, 冯坚. 锆酸镧多孔隔热材料研究进展[J]. 无机材料学报, 2026, 41(4): 421-431.
[7]	刘国晋, 黄昌保, 余学舟, 祁华贝, 胡倩倩, 倪友保, 王振友, 吴海信. KTb₃F₁₀单晶生长及光谱性能研究[J]. 无机材料学报, 2026, 41(3): 370-376.
[8]	李浩, 齐源, 高相东, 张星星, 王金敏. 溶胶凝胶水热法制备耐高温、隔热增强钙掺杂二氧化硅气凝胶[J]. 无机材料学报, 2026, 41(2): 262-272.
[9]	李廷松, 王文丽, 刘强, 王雁斌, 周真真, 胡辰, 李江. Cr³⁺掺杂浓度对YAGG:Ce³⁺,Cr³⁺发光陶瓷余辉性能的影响[J]. 无机材料学报, 2025, 40(9): 1037-1044.
[10]	闫共芹, 王晨, 蓝春波, 洪雨昕, 叶维超, 付向辉. Al掺杂P2型Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂钠离子电池正极材料的制备与电化学性能[J]. 无机材料学报, 2025, 40(9): 1005-1012.
[11]	江宗玉, 黄红花, 清江, 王红宁, 姚超, 陈若愚. 铝离子掺杂MIL-101(Cr)的制备及其VOCs吸附性能研究[J]. 无机材料学报, 2025, 40(7): 747-753.
[12]	柴润宇, 张镇, 王孟龙, 夏长荣. 直接组装法制备氧化铈基金属支撑固体氧化物燃料电池[J]. 无机材料学报, 2025, 40(7): 765-771.
[13]	周阳阳, 张艳艳, 于子怡, 傅正钱, 许钫钫, 梁瑞虹, 周志勇. 通过Bi³⁺自掺杂增强CaBi₄Ti₄O₁₅基陶瓷压电性能[J]. 无机材料学报, 2025, 40(6): 719-728.
[14]	陈莉波, 盛盈, 伍明, 宋季岭, 蹇建, 宋二红. Na和O元素共掺杂氮化碳高效光催化制氢[J]. 无机材料学报, 2025, 40(5): 552-562.
[15]	孙雨萱, 王政, 时雪, 史颖, 杜文通, 满振勇, 郑嘹赢, 李国荣. 缺陷偶极子热稳定性对Fe掺杂PZT陶瓷机电性能影响研究[J]. 无机材料学报, 2025, 40(5): 545-551.