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摘要: 通過溶膠?凝膠（Sol?Gel）法成功合成了納米錳方硼石并對其進行了稀土Eu3+摻雜。使用X射線衍射、透射電子顯微鏡和高分辨透射電子顯微鏡等表征了錳方硼石晶體結構，并通過熒光光譜測試對其發光性能進行了研究。結果表明：合成納米錳方硼石為粒徑小于50 nm的球狀顆粒，與天然錳方硼石的物相結構相同，屬于斜方晶系，與尖晶石類似，（010）晶面的晶面間距為0.8565 nm。在490 nm激發光激發下，天然錳方硼石、合成錳方硼石和稀土Eu3+摻雜錳方硼石晶體中的Mn2+發光，其中發綠光的Mn2+在晶體中占據四面體格位中心，發紅光的Mn2+在晶體占據八面體格位中心。合成的錳方硼石隨激發波長變長，產生發射光譜的紅移現象，有利于實現冷暖發光轉換；在稀土Eu3+摻雜的納米錳方硼石光譜的發光強度得到了提升。Abstract: Chambersite (Mn3B7O13Cl) is both a rare inorganic macromolecular manganese chloroborate and a rare mineral. The chambersite deposit was firstly discovered in Jixian, Tianjin, China, which is the only mineable chambersite deposit in the world. Due to its unique multi-element composition and structure type, it has great application potential as a light-emitting material in biological anti-virus, anti-tumor, and anti-microbial applications, as well as a nuclear-protection and LED applications. However, as yet there are few reports on the material science of chambersite. Rare-earth and transition-group ion-activated borate are important constituent systems in luminescent materials. In this paper, nano-chambersite and rare-earth-element Eu3+-doped nano-chambersite were successfully synthesized by Sol-Gel method. The crystal structure of the nano-chambersite was characterized by X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy. The performance comparison between natural chambersite and synthetic chambersite was provided to provide a basis for the rational development and utilization of chambersite. The results show that the artificially synthesized chambersite has a spherical shape with a particle size of less than 50 nm, and has the same phase structure as natural chambersite. It belongs to the orthorhombic system and has a structure similar to that of spinel. The inter planar spacing of (010) is 0.8565 nm. Under 490 nm excitation light, the natural chambersite, artificially synthesized chambersite, and rare-earth-element Eu3+-doped chambersite crystal all showed a Mn2+ emitting center. The Mn2+ that filled the center of the tetrahedral lattice site of the crystal exhibited a green emission, whereas the Mn2+ that filled the center of the octahedral lattice site of the crystal exhibited a red emission. The artificially synthesized chambersite showed a unique red shift of the emission spectrum with increases in the emitting-light wavelength. This unique phenomenon is beneficial to the conversion of cold and warm luminescence. Eu3+ doping in the artificially synthesized chamversite further increased the intensity of the luminescence.
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圖 1 合成納米錳方硼石（Mn3B7O13Cl）、稀土Eu3+摻雜納米錳方硼石（Mn3B7O13Cl:Eu3+）及天然錳方硼石的XRD譜圖
Figure 1. XRD spectrum of artificial synthesized chambersite (Mn3B7O13Cl), Eu3+ doped chambersite (Mn3B7O13Cl:Eu3+) and natural chambersite
圖 4 合成納米錳方硼石透射表征圖.（a）合成納米錳方硼石HRTEM；（b）反傅里葉變換后計算像
Figure 4. TEM characterization of artificial synthesized Mn3B7O13Cl: (a) HRTEM image of artificial synthesized Mn3B7O13Cl; (b) calculated image after inverse Fourier transform
圖 5 錳方硼石熒光發光性能測試。（a）合成錳方硼石中Mn2+在不同激發波長下的發射光譜，縮小圖為500～550 nm波長范圍內局部放大圖；（b）在激發波長為490 nm下天然錳方硼石、合成錳方硼石及Eu3+摻雜錳方硼石的發射光譜
Figure 5. Fluorescence performance of Mn3B7O13Cl: (a) emission spectra of Mn2+ in artificial synthesized Mn3B7O13Cl under different excitation wavelengths, and the reduced image is a partial enlarged image in the wavelength range of 500–550 nm; (b) emission spectra of natural Mn3B7O13Cl, artificial synthesized Mn3B7O13Cl, and Mn3B7O13Cl:Eu3+ under an excitation wavelength of 490 nm
表 1 晶胞參數對比表
Table 1. Comparison of unit cell parameters
Specimen type a/nm b/nm c/nm Grain size/nm PDF standard card 0.86783 0.86885 1.22963 Artificial synthesized 0.8693 0.8687 1.2279 74.3 Eu3+ doped 0.8680 0.8686 1.2285 73.1 
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表 2 峰值統計表
Table 2. Comparison of peak intensity
Specimen type λgreen /nm Igreen λred/nm Ired Ired/Igreen Natural Mn3B7O13Cl 552.4 1821 739 1917 1.053 Artificially synthesized Mn3B7O13Cl 552.0 1059 739 1351 1.276 Eu3+doped Mn3B7O13Cl 552.2 1458 739 1694 1.162
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