硅酸盐学报

Eu掺杂MgO-P₂O₅-B₂O₃玻璃的光学、发光和闪烁性能

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Okazaki KAI , Nishikawa AKIHIRO , Nakauchi DAISUKE , Kato TAKUMI , Kawaguchi NORIAKI , Yanagida TAKAYUKI

硅酸盐学报 | 先进玻璃与光学材料专题——研究论文 2025,54(4): 1299-1306

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硅酸盐学报 | 先进玻璃与光学材料专题——研究论文 2025, 54(4): 1299-1306

Eu掺杂MgO-P₂O₅-B₂O₃玻璃的光学、发光和闪烁性能

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Okazaki KAI, Nishikawa AKIHIRO, Nakauchi DAISUKE, Kato TAKUMI, Kawaguchi NORIAKI, Yanagida TAKAYUKI

作者信息

奈良先端科学技术学院（NAIST），奈良县生驹市 630-0192，日本

KAI Okazaki（1998—），男，博士研究生。

KAI Okazaki (1998-), male, Doctoral candidate. E-mail: okazaki.kai.of0@ms.naist.jp

Optical, Luminescence, and Scintillation Properties of Eu-Doped MgO-P₂O₅-B₂O₃Glasses

Okazaki KAI, Nishikawa AKIHIRO, Nakauchi DAISUKE, Kato TAKUMI, Kawaguchi NORIAKI, Yanagida TAKAYUKI

Affiliations

Nara Institute of Science and Technology (NAIST), 8916-5 Takayama-Cho, Ikoma City, Nara 630-0192, Japan

出版时间: 2025-11-28 doi: 10.14062/j.issn.0454-5648.20250560

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摘要

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通过熔融淬火法制备了未掺杂和掺杂Eu的MgO-P₂O₅-B₂O₃玻璃，并研究了它们的光学和闪烁性能。制备的样品具有70%～90%的透射率。由于在紫外-可见光和X射线下Eu²⁺发生4f⁶5d¹-4f⁷跃迁并产生发光。当在320 nm激发、在350～560 nm监测时0.1%、0.3%、1.0%和2.0%（摩尔分数）Eu掺杂的MgO-P₂O₅-B₂O₃玻璃的光致发光量子产率分别为46.7%、37.2%、20.4%和9.3%。在未掺杂、0.1%、0.3%、1.0%和2.0%掺杂Eu的样品中，计算出在2 ms X射线照射后20 ms的余辉水平分别为1700×10^-6、4500×10^-6、3400×10^-6、800×10^-6和160×10^-6。使用合成的MgO-P₂O₅-B₂O₃玻璃测量²⁴¹Am α射线脉冲高度谱。根据比较样品和参照物（Gd₂SiO₅、LY：8000光子／MeV）的全吸收峰位置，0.3%、1.0%和2.0%掺铕样品的光产额（LY）计算分别为70、150和40个光子／5.5 MeV。

关键词

闪烁 / 光致发光 / 二价铕离子 / 辐射检测

Abstract

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Introduction

Scintillators are functional materials that immediately emit low-energy photons after absorbing high-energy ionizing radiations. Glasses have advantages as a material form for scintillator use, such as low manufacturing costs, ease of formability, high optical transparency, and high compositional tunability. A ⁶Li-glass scintillator doped with Ce is a commercial glass scintillator, and it has been used for thermal neutron detections owing to ⁶Li(n,α)³H neutron capture reactions. In general, the ³He counter is used in practice for neutron detections; however, the depletion of the ³He supply has driven vigorous research and development of alternative materials. ¹⁰B-contained glasses have an advantage of their large thermal neutron capture cross section (3840 barn). In this study, we focused on MgO-P₂O₅-B₂O₃ glass systems. They are composed of light elements; hence, neutron detection signals can be easily distinguished from noise due to X- and γ-rays. Furthermore, alkali-earth-embedded P₂O₅-B₂O₃ glasses realize high optical transparency with good chemical durability. As luminescence centers, Eu was selected. Eu exists in two different states: Eu²⁺ in reduction states and Eu³⁺ in oxidation states. The former shows broad emission bands with fast decay times of ~μs, whereas the latter shows sharp emission bands with slow decay times of ~ms. In general, Eu³⁺ is governed in the glasses prepared in an air atmosphere; however, alkali-earth-embedded P₂O₅-B₂O₃ glasses can exhibit Eu²⁺ owing to the localized reducing atmosphere generated by NH₃ derived from the raw material (NH₄H₂PO₄). Here, Eu-doped MgO-P₂O₅-B₂O₃ glasses with various concentrations of Eu were synthesized by the conventional melt quenching technique in air, and their optical, photoluminescence (PL), and scintillation properties were examined.

Methods

Undoped and 0.1%, 0.3%, 1.0%, and 2.0% (in mole fraction) Eu-doped 25MgO-30P₂O₅-45B₂O₃ (MPB) glasses were synthesized by the melt quenching method. Raw materials were homogeneously mixed and transferred into an alumina crucible. The powders were melted at 1100 ℃ for 1 h with an electrical furnace in air. The melt was flowed onto a preheated stainless-steel plate to quench, and pressed into batches. After that, the glasses were annealed at 400 ℃ for 1 h to remove thermal and mechanical strains. The surfaces of the glasses were polished for the following optical and scintillation measurements. The glass transition temperature (T_g) of the undoped sample was measured with a TG-DTA system. The powder X-ray diffraction (XRD) patterns were measured using a diffractometer. Diffuse transmission spectra were measured using a spectrophotometer (Shimadzu, SolidSpec-3700). PL excitation and emission spectra, PL quantum yields (QYs), and PL decay curves were measured using a Quantaurus-QY and Quantaurus-τ. Scintillation spectra, scintillation decay curves, and afterglow curves under X-ray irradiations, and pulse height spectra of ²⁴¹Amα-rays and ¹³⁷Cs γ-rays were measured with our original setups.

Results and discussion

The appearances of undoped and Eu-doped MPB glasses were transparent and included some bubbles. Under ultraviolet light at 360 nm, Eu-doped samples showed bluish-red light. Some parts of the glasses were crushed into powder and used for the XRD measurements. Precipitations of crystalline phases were not observed in the XRD patterns; hence, the prepared samples formed glass phases with no periodical structures. T_g of the undoped glass was estimated to be 535 ℃. The transmittances of all the glasses were 70%-90% at 400-700 nm. Both the undoped and Eu-doped samples showed absorption peaks at 200-250 nm; hence, this can be due to the hosts. In addition, absorption peaks emerged at 250-400 nm in Eu-doped samples. The absorption bands at 250-280 nm and 280-400 nm originated from the 4f⁷-4f⁶5d¹ (T_2g and E_g) transitions of Eu²⁺, respectively. An absorption peak due to the ⁷F₁-⁵D₃ transitions of Eu³⁺ was confirmed at 415 nm in the spectra of 2% Eu. A broad emission band due to the electronic transitions of Eu²⁺ was observed at 400-600 nm under excitation bands at 250-410 nm in the Eu-doped samples. Generally, emissions due to Eu²⁺ are difficult to observe in the glasses prepared in air because of the oxidizing atmosphere. The emissions appeared owing to the localized reduction atmosphere, which derived from NH₄H₂PO₄and (NH₄)₂O·5B₂O₃·8H₂O. When excitation and monitored wavelengths were respectively set to 340 nm and 420 nm, the PL decay curves were fitted by a sum of two exponential functions. The PL decay time constants of both the fast (0.2-0.5 μs) and slow (0.7-1.2 μs) components were similar to those of other Eu-doped phosphors; hence, they are reasonable as 4f⁶5d¹(T_2g)-4f⁷ and 4f⁶5d¹(E_g)-4f⁷ transitions of Eu²⁺. Eu-doped samples showed emission peaks at 350-500 nm under X-ray irradiations. These emission wavelengths were consistent with those of the PL spectra. Afterglow levels (AL) of undoped and 0.1%, 0.3%, 1.0%, and 2.0% Eu-doped glasses at 20 ms passed after X-ray irradiation of 2 ms were respectively estimated to be 1700×10^-6, 4500×10^-6, 3400×10^-6, 800×10^-6, and 160×10^-6. Pulse height spectra of ²⁴¹Am α-rays (5.5 MeV) were measured using the prepared MPB glasses. Eu-doped glasses showed clear full energy absorption peaks. Light yields (LY) of 0.3%, 1.0%, and 2.0% Eu-doped MPB glasses were respectively calculated to be 70, 150 photons/5.5 MeV, and 40 photons/5.5 MeV.

Conclusion

Eu-doped MPB glasses were synthesized by the conventional melt quenching method. All the samples showed halo peaks with no periodic patterns in XRD measurements. The transmittances were 70%-90%, and absorptions due to electronic transitions of Eu²⁺ and Eu³⁺ were observed. All the samples showed luminescence, which originated from the 4f⁶5d¹-4f⁷ transitions of Eu²⁺. PL QYs of 0.1%, 0.3%, 1.0%, and 2.0% Eu-doped samples were respectively calculated to be 46.7%, 37.2%, 20.4%, and 9.3% when monitored at 350-560 nm under excitation at 320 nm. ALs at 20 ms passed after X-ray irradiations of 2 ms were obtained to be 1700×10^-6, 4500×10^-6, 3400×10^-6, 800×10^-6, and 160×10^-6 in undoped, 0.1%, 0. 3%, 1.0%, and 2.0% Eu-doped samples, respectively. Pulse height spectra of ²⁴¹Am α-rays were measured using the prepared samples. LYs of 0.3%, 1.0%, and 2.0% Eu-doped samples were respectively determined to be 70, 150 photons/5.5 MeV, and 40 photons/5.5 MeV.

Key words

scintillation / photoluminescence / divalent europium ion / radiation detection

引用本文

Okazaki KAI, Nishikawa AKIHIRO, Nakauchi DAISUKE, Kato TAKUMI, Kawaguchi NORIAKI, Yanagida TAKAYUKI. Eu掺杂MgO-P₂O₅-B₂O₃玻璃的光学、发光和闪烁性能. 硅酸盐学报, 2025 , 54 (4) : 1299 -1306 . DOI: 10.14062/j.issn.0454-5648.20250560

Okazaki KAI, Nishikawa AKIHIRO, Nakauchi DAISUKE, Kato TAKUMI, Kawaguchi NORIAKI, Yanagida TAKAYUKI. Optical, Luminescence, and Scintillation Properties of Eu-Doped MgO-P₂O₅-B₂O₃Glasses[J]. Journal of the Chinese Ceramic Society, 2025 , 54 (4) : 1299 -1306 . DOI: 10.14062/j.issn.0454-5648.20250560

基金

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生物医学工程研究中心合作研究项目，中部电工技术研究基金和岛津科学基金

参考文献

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2025年第54卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250560

接收时间：2025-07-18
首发时间：2026-05-20
出版时间：2025-11-28

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收稿日期：2025-07-18
修回日期：2025-09-16

基金

生物医学工程研究中心合作研究项目，中部电工技术研究基金和岛津科学基金

作者信息

奈良先端科学技术学院（NAIST），奈良县生驹市 630-0192，日本

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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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