KTb3F10单晶生长及光谱性能研究

doi:10.15541/jim20250230

无机材料学报 ›› 2026, Vol. 41 ›› Issue (3): 370-376.DOI: 10.15541/jim20250230 CSTR: 32189.14.jim20250230

KTb₃F₁₀单晶生长及光谱性能研究

刘国晋¹^,²(), 黄昌保¹^,³(), 余学舟¹, 祁华贝¹^,², 胡倩倩¹^,², 倪友保¹^,³, 王振友¹, 吴海信¹()

1.中国科学院合肥物质科学研究院安徽光学精密机械研究所, 安徽省光子器件与材料重点实验室, 合肥 230031
2.中国科学技术大学, 合肥 230026
3.江淮前沿技术协同创新中心, 合肥 230000

收稿日期:2025-05-27 修回日期:2025-06-10 出版日期:2025-07-16 网络出版日期:2025-07-16
通讯作者: 黄昌保, 副研究员. E-mail: cbhuang@aiofm.ac.cn;
吴海信, 研究员. E-mail: hxwu@aiofm.ac.cn
作者简介:刘国晋(1995-), 男, 博士研究生. E-mail: lgjustc@mail.ustc.edu.cn
基金资助:
国家重点研发计划(2021YFB3601503)

Growth and Spectral Property of KTb₃F₁₀ Single Crystal

LIU Guojin¹^,²(), HUANG Changbao¹^,³(), YU Xuezhou¹, QI Huabei¹^,², HU Qianqian¹^,², NI Youbao¹^,³, WANG Zhenyou¹, WU Haixin¹()

1. Anhui Provincial Key Laboratory of Photonic Devices and Material, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China
2. University of Science and Technology of China, Hefei 230026, China
3. Jianghuai Advanced Technology Center, Hefei 230000, China

Received:2025-05-27 Revised:2025-06-10 Published:2025-07-16 Online:2025-07-16
Contact: HUANG Changbao, associate professor. E-mail: cbhuang@aiofm.ac.cn;
WU Haixin, professor. E-mail: hxwu@aiofm.ac.cn
About author:LIU Guojin (1995-), male, PhD candidate. E-mail: lgjustc@mail.ustc.edu.cn
Supported by:
National Key Research and Development Program of China(2021YFB3601503)

摘要/Abstract

摘要：

KTb₃F₁₀(KTF)晶体具有Tb³⁺离子浓度高、热光系数小、声子能量低等优点, 在绿光和黄光波段展现出高效激光输出潜力。然而, 其非一致熔融特性、原料易潮解、高温下组分易挥发以及氟化物腐蚀性等问题, 成为制约高品质KTF晶体生长的关键障碍。本研究致力于探索一种有效的方法, 克服上述难题, 以生长出高品质KTF晶体并系统表征其光学性能。采用优化的垂直布里奇曼法, 并结合激光真空密封铂坩埚技术, 有效隔绝了原料与水氧杂质的接触, 同时, 密封的生长环境极大地抑制了晶体生长过程中的组分偏离现象。通过该创新工艺, 成功生长出尺寸为φ16 mm×30 mm的KTF毛坯晶体。KTF晶体(111)晶面的X射线摇摆曲线半高宽为0.08°, 显示出较高的晶体完整性。热分析表明KTF晶体在高温下存在明显的挥发行为。光谱测试显示, KTF晶体在400~1600 nm波段的平均透过率>90%, 1064 nm处吸收系数<0.007 cm^-1, 具有较低的光学损耗。Tb³⁺离子⁵D₄能级的荧光寿命为4.82~4.99 ms, 较氧化物基质长3~5倍, 这归因于低声子氟化物基质对非辐射弛豫的抑制。本研究成功建立了一种可行的KTF晶体生长方法, 为KTF晶体及同类型三元氟化物的可控生长提供了一种新的技术路径, 为KTF晶体在黄绿光波段的高效输出应用提供了有益参考。

关键词: KTb₃F₁₀, 垂直布里奇曼法, 光谱性能, 荧光寿命

Abstract:

KTb₃F₁₀ (KTF) crystal, characterized by its high Tb³⁺ ion concentration, low thermo-optic coefficient and low phonon energy, exhibits significant potential for efficient laser emission in the green and yellow wavelength ranges. However, challenges such as incongruent melting behavior, hygroscopicity of raw materials, high-temperature compositional volatility, and corrosive nature of fluorides have severely hindered the growth of high-quality KTF crystals. This study aims to develop an effective approach to address these issues, achieve the growth of high-quality KTF crystals, and characterize their optical properties. An optimized vertical Bridgman method integrated with a laser-sealed platinum crucible technique under vacuum was employed. This innovative approach effectively shielded the raw materials from water and oxygen contamination while suppressing compositional deviation during crystal growth through a sealed environment. As a result, blank KTF crystals with dimensions of φ16 mm×30 mm were successfully grown, and their relevant spectral properties were characterized. X-ray rocking curve of the (111) plane showed a full width at half maximum of 0.08°, indicating high crystalline perfection. Thermal analysis indicated significant volatilization of KTF at high temperatures. Spectral tests revealed an average transmittance of >90% in the 400-1600 nm range and an absorption coefficient of <0.007 cm^-1 at 1064 nm, demonstrating minimal optical loss suitable for high-power laser applications. Fluorescence lifetime was 4.82-4.99 ms for the Tb³⁺ion at the ⁵D₄ energy level, which is 3-5 times longer than that in oxide matrices. This superiority is attributed to the suppression of non-radiative relaxation by the low-phonon fluoride matrix, enhancing the energy storage efficiency for laser emission. Based on above data, this study has successfully established a viable growth method for KTF crystals, providing a new technical pathway for the controllable synthesis of KTF and other ternary fluoride materials. All these results provide valuable insights for the high-efficiency application of KTF crystals in yellow-green laser emission.

Key words: KTb₃F₁₀, vertical Bridgman method, spectral property, fluorescence lifetime

中图分类号:

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.

LIU Guojin, HUANG Changbao, YU Xuezhou, QI Huabei, HU Qianqian, NI Youbao, WANG Zhenyou, WU Haixin. Growth and Spectral Property of KTb₃F₁₀ Single Crystal[J]. Journal of Inorganic Materials, 2026, 41(3): 370-376.

图/表 13

图1 KF-TbF3二元体系相图[23]

Fig. 1 Phase diagram of KF-TbF3 binary systems[23]

图2 KTF晶体生长结果

Fig. 2 Results of KTF crystal growth (a) KTF blank crystal sliced along the central axis; (b) Oriented (111) plane sample

图3 KTF晶胞结构[26]

Fig. 3 Cell structure of KTF crystal[26]

图4 KTF单晶粉末的XRD图谱及精修结果

Fig. 4 XRD patterns and Rietveld refinement results of KTF single crystal powder

表1 KTF单晶结构精修的晶体数据

Table 1 Crystallographic data from structural refinement of KTF single crystal

Cell parameter	a/nm	V/nm³	Density/(g·cm^-3)	R_wp/%	R_p/%	χ²
KTF single crystal	1.1662(4)	1.58591(16)	5.478	11.05	7.48	1.41
PDF#04-006-4631	1.168	1.59341	5.885	11.05	7.48	1.41

图5 KTF单晶(111)晶面的单晶摇摆曲线

Fig. 5 X-ray rocking curve of (111) plane for KTF single crystal

图6 KTF单晶的TG-DSC热分析曲线

Fig. 6 TG-DSC thermal analysis curves of KTF single crystal

图7 KTF单晶的紫外-可见-近红外透过光谱

Fig. 7 UV-Vis-NIR transmission spectrum of KTF single crystal

图8 KTF单晶的吸收光谱

Fig. 8 Absorption spectrum of KTF single crystal

图9 Tb3+离子的能级结构与特征跃迁

Fig. 9 Energy levels and characteristic transitions of Tb3+ ions

图10 KTF晶体中Tb3+离子的荧光发射光谱

Fig. 10 Fluorescence emission spectra of Tb3+ in KTF crystal Colorful figure is available on website

图11 在351 nm泵浦激发下KTF晶体在不同发射波长处的荧光衰减曲线

Fig. 11 Fluorescence decay curves of KTF crystal under 351 nm excitation at different emission wavelengths (a) 488 nm; (b) 545 nm; (c) 584 nm; (d) 622 nm. All curves were fitted using a single-exponential function

表2 Tb3+在不同晶体中的5D4能级寿命(τexpt)

Table 2 Energy level 5D4 lifetime (τexpt) of Tb3+ in different crystals

Crystal	τ_expt/ms	Ref.	Crystal	τ_expt/ms	Ref.
KTb₃F₁₀	4.82-4.99	This work	Tb: KY₃F₁₀	4.8	[11]
Tb_0.81Ca_0.19F_2.81	6.9	[30]	Tb: Y₂Mg₂Al₂Si₂O₁₂	0.58-1.72	[32]
Tb: LiYF₄	4.9	[31]	Tb: SrGd₂Al₂O₇	1.56-2.80	[33]
Tb: LiLuF₄	~5.0	[8]

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KTb₃F₁₀单晶生长及光谱性能研究

Growth and Spectral Property of KTb₃F₁₀ Single Crystal

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