硅酸盐学报

镍离子激活超宽带近红外发光微晶玻璃研究进展

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高志刚 ¹ , 赵瑞 ¹ , 肖静 ¹ , 崔鲁贵 ² , 王慈 ² , 钱森 ³ , 任晶 ²

硅酸盐学报 | 综合评述 2024,52(5): 1739-1748

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硅酸盐学报 |综合评述 2024 , 52 (5) : 1739 -1748

镍离子激活超宽带近红外发光微晶玻璃研究进展

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高志刚¹, 赵瑞¹, 肖静¹, 崔鲁贵², 王慈², 钱森³, 任晶²

作者信息

^1．泰山学院物理与电子工程学院，山东泰安 271021

^2．哈尔滨工程大学物理与光电工程学院，哈尔滨 150001

^3．中国科学院高能物理研究所，北京 100049

通讯作者:

肖静（1979—），女，博士，教授；

钱森（1981—），男，博士，研究员；

任晶（1981—），男，博士，教授。

作者简介:

高志刚（1990—），男，博士，副教授。

Research Progress on Ni²⁺-Activated Ultra-Broadband Near-Infrared Emission Glass-Ceramics

Zhigang GAO¹, Rui ZHAO¹, Jing XIAO¹, Lugui CUI², Ci WANG², Sen QIAN³, Jing REN²

Affiliations

^1.School of Physics and Electronic Engineering, Taishan University, Tai'an 271021, Shandong, China

^2.School of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, China

^3.Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

Corresponding Author:

XIAO Jing (1979-), female, Ph.D., Professor. E-mail: xiaojingzx@163.com;

QIAN Sen (1981-), male, Ph.D., Professor. qians@ihep.ac.cn;

REN Jing (1981-), male, Ph.D., Professor. ren.jing@hrbeu.edu.cn

GAO Zhigang (1990-), male, Ph.D., Associate Professor. E-mail: realgaozg@gmail.com

出版时间: 2024-05-20 doi: 10.14062/j.issn.0454-5648.20230704

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摘要

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处在六配位八面体晶体场的过渡金属镍离子（Ni²⁺）具有超宽带近红外发光特性，其荧光半高宽是传统稀土离子（如Pr³⁺、Er³⁺）的6~8倍。Ni²⁺激活的近红外增益材料有望应用于宽带光放大器和可调谐激光器，引发了中国内外广泛关注。Ni²⁺掺杂晶体具有极高的发光效率，但晶体存在制备工艺复杂、机械加工困难和难以成纤等问题，限制了此类材料在光纤放大器和激光器领域的应用。玻璃具有易加工和成纤的优点，但Ni²⁺在玻璃中缺少合适的晶体场（配位场）环境，无法产生高效近红外发光。通过对玻璃进行热处理，可以在玻璃内部原位生成出不同类型的纳米晶体，即获得纳米晶体复合的微晶玻璃，可以为Ni²⁺提供必需的晶体场。同时，控制玻璃内部生长的晶粒尺寸，使其远小于可见光波长（如小于30 nm），可有效减弱瑞利散射，使微晶玻璃具有较低的光学损耗，满足光子器件实际应用要求。讨论了Ni²⁺激活微晶玻璃的发光机理以及Ni²⁺激活晶体、单相微晶玻璃、双相微晶玻璃和微晶玻璃光纤在超宽带近红外发光方面的研究进展，同时展望了Ni²⁺激活超宽带近红外发光微晶玻璃未来研究的发展方向。

关键词

过渡金属离子 / 微晶玻璃 / 宽带发光 / 光纤放大器 / 近红外光源

Abstract

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Transition metal nickel ions (Ni²⁺) situated in a six-coordinate octahedral crystal field exhibit a ultra-broad near-infrared (NIR) luminescence, with a fluorescence half width at half maximum (HWHM) 6-8 times that of rare-earth (RE) element ions like Pr³⁺ and Er³⁺. Ni²⁺-activated NIR gain materials can be used in broadband optical amplifiers and tunable lasers, which have attracted attention. Despite their impressive luminescent efficiency, Ni²⁺-doped crystals have some limitations in optical fiber amplifier and laser applications due to their intricate fabrication processes, machining, and fiber formation. Glass offers some advantages in processing and fiber formation, but lacks a conducive crystal field (coordination field) environment for Ni²⁺ to achieve an efficient NIR luminescence. Various types of nanocrystals can be generated in-situ within the glass via subjecting glass to heat treatment, resulting in the formation of nanocrystalline composite glass-ceramics (GCs). Also, a precise control of grain size within the glass to dimensions smaller than the visible light wavelength (e.g., less than 30 nm) effectively mitigates the Rayleigh scattering, endowing GCs with reduced optical losses that meet the practical demands of photonic devices.

Johnson, et al. investigated the optical properties of Ni²⁺. They prepared MgF₂ crystals doped with Ni²⁺ and observed fluorescence emission characteristics and optical laser oscillation phenomena under pulse xenon lamp or tungsten lamp excitation at low temperatures (i.e., 20, 77 K, and 85 K). Ohishi et al. reported Ni²⁺ activated LiGa₅O₈ nanocrystalline GCs with a broadband fluorescence emission centered at 1.3 μm with a half-width greater than 300 nm under 976 nm excitation. The lifetimes at 5 k and 300 k were greater than 900 μs and 500 μs, respectively, with internal and external quantum efficiencies of 100% and 9%, respectively. This emission was attributed to the transition of Ni²⁺ from ³T_2g(³F)→³A_2g(³F) level in the LiGa₅O₈ crystal octahedral coordination. Zhou et al. reported the phenomenon of NIR light amplification in Ni²⁺ doped β-Ga₂O₃ nanocrystalline transparent GCs. Zhou et al. designed a special glass system with the composition of SiO₂/Na₂O/Ga₂O₃/LaF₃ = 51%/15%/20%/14% (in mole). This glass system can orderly precipitate LaF₃ and Ga₂O₃ nanocrystals. For co-doping with Er³⁺ and Ni²⁺, the two active ions can enter the two different nanocrystals, respectively, the physical distance between the two active ions and the local crystal field changes effectively inhibit the energy transfer between the two different active ions, achieving the near-infrared ultra-wideband luminescence of an integrated multi-color visible and Er³⁺/Ni²⁺ composite.

Summary and prospects

The existing fluorescence regulation of Ni²⁺-doped GCs is studied, having a great potential in broadband amplifiers, tunable lasers, non-invasive sensing, infrared night vision sources, and infrared medical diagnosis. Numerous studies indicate that 1) the NIR emission band and bandwidth of Ni²⁺ can be regulated via controlling the types (oxides, fluorides) and modes (single phase or dual phase) of crystals in GCs; 2) the luminescence intensity of Ni²⁺ can be further enhanced by energy transfer through sensitizers such as Nd³⁺, Yb³⁺, Cr³⁺, etc..; 3) the luminescence intensity of Ni²⁺ can be also enhanced by optical field regulation, such as using noble metal nanocrystals to improve the collection efficiency of pump light.

However, Ni²⁺-activated transparent GCs still have some challenges. The doping concentration of Ni²⁺ in microcrystalline glass and microcrystalline glass fibers is relatively low, usually less than 0.2% (in mole fraction), resulting in low NIR absorption coefficients; The matrix glasses that can carry Ni²⁺ activation are still limited. Exploring multi-component glass matrices that can precipitate new types of crystal phases is one of the main tasks; Residual Ni²⁺ at the glass phase or glass-crystal phase interface still accounts for a large proportion. Some strategies are needed to ensure that most Ni²⁺ enters the target crystals, further improving its infrared optical performance; The gain coefficient of Ni²⁺-doped microcrystalline glass/fiber is relatively low (<0.3 cm^-1) due to the limited volume ratio of nanocrystals in the glass (i.e., crystallization rate) and the influence of surface/interface defects of nanocrystals. Meanwhile, efficient positive feedback cannot be formed due to the lack of high-quality resonant cavities, resulting in only room-temperature luminescence of Ni²⁺, and no laser emission is achieved yet. The prerequisite for achieving laser emission is to obtain laser materials with sufficient gain.

The Purcell effect can accelerate the radiation relaxation process of luminescent materials, resulting in an increased radiation probability and a correspondingly increased quantum efficiency of photoluminescence. Based on whispering gallery mode (WGM) glass microspheres, light can be confined in the micron-scale cavity for a long time based on the principle of total reflection. Therefore, it has an extremely high quality factor (i.e., ≥10⁵) and minimal mode volume (i.e., ≤10³ μm³), which can fully utilize the Purcell effect to enhance the interaction between light and matter. With the unique advantages of the WGM glass microsphere cavity, the preparation of a new Ni²⁺-doped microcrystalline glass microsphere laser provides an effective way to break through the physical bottleneck of room-temperature Ni²⁺ laser emission and develop low-threshold, ultra-broadband near-infrared multi-wavelength micro-lasers.

Key words

transition metal ions / glass-ceramics / ultra-broadband luminescence / fiber amplifiers / near-infrared light source

引用本文

高志刚, 赵瑞, 肖静, 崔鲁贵, 王慈, 钱森, 任晶. 镍离子激活超宽带近红外发光微晶玻璃研究进展. 硅酸盐学报, 2024 , 52 (5) : 1739 -1748 . DOI: 10.14062/j.issn.0454-5648.20230704

Zhigang GAO, Rui ZHAO, Jing XIAO, Lugui CUI, Ci WANG, Sen QIAN, Jing REN. Research Progress on Ni²⁺-Activated Ultra-Broadband Near-Infrared Emission Glass-Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (5) : 1739 -1748 . DOI: 10.14062/j.issn.0454-5648.20230704

基金

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国家自然科学基金(62305244; 62374112)
山东省自然科学基金(ZR2021QE060)
山东省高等学校青年创新团队(2022KJ258)

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2024年第52卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230704

接收时间：2023-09-09
首发时间：2026-10-22
出版时间：2024-05-20

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出版历史

收稿日期：2023-09-09
修回日期：2023-09-19

基金

国家自然科学基金(62305244; 62374112)

山东省自然科学基金(ZR2021QE060)

山东省高等学校青年创新团队(2022KJ258)

作者信息

^1．泰山学院物理与电子工程学院，山东泰安 271021

^2．哈尔滨工程大学物理与光电工程学院，哈尔滨 150001

^3．中国科学院高能物理研究所，北京 100049

通讯作者:

肖静（1979—），女，博士，教授；

钱森（1981—），男，博士，研究员；

任晶（1981—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230704

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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