无机材料学报

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Ho:BaF2晶体在近红外-中红外波段光谱性能分析

钱新宇1, 王无敌1, 郭俊尧1, 任永春1, 董建树1, 王庆国1, 唐慧丽1, 张晨波1, 徐晓东2, 董永军3, 华伟4, 徐军1   

  1. 1.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;
    2.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;
    3.上海芯飞睿科技有限公司,上海 300444;
    4.宁波镭晶科技有限公司,宁波 315500
  • 收稿日期:2025-09-02 修回日期:2025-10-08
  • 作者简介:钱新宇(1998-), 男, 博士研究生. E-mail: 894742295@qq.com
  • 基金资助:
    国家重点研发计划(2022YFB3605701,2023YFB3507401);国家自然科学基金(62275198,52032009)

Spectroscopic Analysis of Ho:BaF₂ Crystals in the NIR to MIR Spectral Region

QIAN Xinyu1, WANG Wudi1, GUO Junyao1, REN Yongchun1, DONG Jianshu1, WANG Qingguo1, TANG Huili1, ZHANG Chenbo1, XU Xiaodong2, DONG Yongjun3, HUA Wei4, XU Jun1   

  1. 1. Institute for Advanced Study, School of Physical Science and Engineering, Key Laboratory of Advanced Micro-Structured Materials, Tongji University, Shanghai 200092, China;
    2. School of Physics and Electronic Engineering, Jiangsu Provincial Key Laboratory of Advanced Laser Materials and Devices, Jiangsu Normal University, Xuzhou 221116, China;
    3. Shanghai Xinfeirui Technology Co., Ltd., Shanghai 300444, China;
    4. Ningbo Leijing Technology Co., Ltd., Ningbo 315500, China
  • Received:2025-09-02 Revised:2025-10-08
  • About author:QIAN Xinyu (1998-), male, PhD candidate. E-mail: 894742295@qq.com
  • Supported by:
    National Key R&D Program of China (2022YFB3605701, 2023YFB3507401); National Natural Science Foundation of China (62275198, 52032009)

摘要: 1~3 μm红外激光在医疗、环境监测和高功率激光系统中具有重要应用价值,其中Ho³⁺离子因其覆盖近红外至中红外多个发射通道而受到广泛关注。本工作系统研究Ho³⁺:BaF₂晶体的结构与光谱特性,并筛选不同发射波段的最佳掺杂浓度,以实现高效多波段激光输出。采用温度梯度法(Temperature Gradient Technique, TGT)成功生长出原子比0.5%-3.0% Ho³⁺:BaF₂单晶。通过XRD和ICP-AES进行结构和组分分析,并利用吸收光谱、荧光光谱和寿命测试表征其光谱性能。同时结合Judd-Ofelt理论计算辐射跃迁参数。所有晶体均呈现立方萤石结构,理论掺杂浓度和实际掺杂浓度接近1且分布均匀。光谱分析表明,~1.2 μm(⁵I₆→⁵I₈)和~2.05 μm(⁵I₇→⁵I₈)的最优掺杂浓度为原子比2.0%(分别对应Q=24.29×10⁻²¹ cm²·ms和Q=67.53×10⁻²¹ cm²·ms),而~2.85 μm(⁵I₆→⁵I₇)的最优浓度为原子比1.0%(Q=44.52×10⁻²¹ cm²·ms)。其中,BaF₂基质低声子能量(~346 cm⁻¹)及抗Ho³⁺离子团簇形成倾向较弱特性使其在~2.05 μm处获得了3.81×10⁻²¹ cm²的最大发射截面,性能优于YAG、CaF₂等传统基质。相较于氧化物基质,BaF₂晶体具有更低的无辐射损耗和更强的抗浓度猝灭能力,有助于实现更高有效掺杂浓度与稳定的多波段激光输出。Ho:BaF₂晶体展现出作为高效多波段红外激光增益介质的巨大潜力。

关键词: 氟化钡晶体, 钬离子掺杂, 中红外激光, 光谱性能

Abstract: Infrared lasers in the 1-3 μm region are increasingly important for applications in medical treatment, atmospheric monitoring, and high-power laser systems. Holmium ions (Ho³⁺) are particularly attractive because of their multiple emission channels covering near to mid infrared ranges. This work aims to systematically evaluate the structural and spectroscopic properties of Ho:BaF₂ crystals and determine the optimal doping concentrations for efficient multi-band laser operation. High-quality Ho:BaF₂ single crystals with concentrations of 0.5%-3.0% (in atomic) were grown using the temperature gradient technique (TGT). Structural characterization was performed by XRD and ICP-AES, while spectroscopic properties were analyzed via absorption, fluorescence, and lifetime measurements. Judd-Ofelt analysis was further applied to calculate radiative parameters. All samples exhibited pure cubic fluorite structures, with doping segregation ratios close to unity and uniform Ho³⁺ distribution. Spectroscopic evaluation revealed optimal doping concentrations of 2.0% (in atomic) for ~1.2 μm (⁵I₆→⁵I₈, Q=24.29×10⁻²¹ cm²·ms) and ~2.05 μm (⁵I₇→⁵I₈, Q=67.53×10⁻²¹ cm²·ms), and 1.0% (in atomic) for ~2.85 μm (⁵I₆→⁵I₇, Q=44.52×10⁻²¹ cm²·ms). The BaF₂ host, with its low phonon energy (~346 cm⁻¹) and anti-clustering characteristics, enabled enhanced emission performance, including a maximum emission cross-section of 3.81×10⁻²¹ cm² at ~2.05 μm. These results outperform traditional hosts such as YAG and CaF₂. Compared to oxide hosts, BaF₂ offers superior lifetime, reduced non-radiative losses, and greater resistance to concentration quenching. The findings indicate that Ho:BaF₂ supports higher effective doping levels, making it particularly promising for high-power and ultrafast laser applications. Ho:BaF₂ crystals demonstrate excellent potential as efficient, multi-wavelength infrared laser gain media.

Key words: BaF2 crystals, holmium doping, mid-infrared lasers, spectroscopic characteristics

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