Er3+掺杂Li2O-SrO-ZnO-Bi2O3玻璃中Er3+离子在1.53 μm处的荧光发射特性

采用传统的熔融法制备了Er~(3+)掺杂的新型铋酸盐玻璃(Li_2O-SrO-ZnO-Bi_2O_3,LSZB),并对其光谱性质进行了表征,分析了玻璃的拉曼光谱、吸收光谱、荧光光谱,利用Judd-Ofelt理论研究了其荧光特性。LSZB玻璃样品中Er~(3+)的~4I_(13/2)→~4I_(15/2)跃迁发射峰位于1.53 μm处,半高宽约为78 nm。样品中Er~(3+)的~4I_(13/2)能级寿命为2.848 ms,量子效率为99.93%,受激发射截面达到9.76×10~(-21)cm~2。以上结果显示,Er~(3+)掺杂LSZB玻璃有良好的光谱特性。     

New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures

A series of polychalcogenotrimethylsilane complexes Ar(CH₂ESiMe₃)_n, (Ar=aryl; E=S, Se; n=2, 3, and 4) can be prepared from the corresponding polyorganobromide and M[ESiMe₃] (M=Na, Li). These represent the first examples of the incorporation of such a large number of reactive ?ESiMe₃ moieties onto an organic molecular framework. They are shown to be convenient reagents for the preparation of the polyferrocenylseleno‐ and thioesters from ferrocenoyl chloride. The synthesis, structures, and spectroscopic properties of the new silyl chalcogen complexes 1,4‐(Me₃SiECH₂)₂(C₆Me₄) (E=S, 1 ; E=Se, 2 ), 1,3,5‐(Me₃SiECH₂)₃(C₆Me₃) (E=S, 3 ; E=Se, 4 ) and 1,2,4,5‐(Me₃SiECH₂)₄(C₆H₂) (E=S, 5 ; E=Se, 6 ) and the polyferrocenyl chalcogenoesters [1,4‐{FcC(O)ECH₂}₂(C₆Me₄)] (E=S, 7 ; E=Se, 8 ), [1,3,5‐{FcC(O)ECH₂}₃(C₆Me₃)] (E=S, 9 ; E=Se, 10 ) and [1,2,4,5‐{FcC(O)ECH₂}₄(C₆H₂)] (E=S, 11 illustrated; E=Se, 12 ) are reported. The new polysilylated reagents and polyferrocenyl chalcogenoesters have been characterized by multinuclear NMR spectroscopy (¹H, ¹³C, ⁷⁷Se), electrospray ionization mass spectrometry and, for complexes 1 , 2 , 3 , 4 , 7 , 8 , and 11 , single‐crystal X‐ray diffraction. The cyclic voltammograms of complexes 7 – 11 are presented.     

Optical Spectroscopy and Excited-State Dynamics of Eu3+-Doped Bismuth Borate Glasses Containing CuO

Bismuth borate glasses containing phosphors and luminescent rare-earths are of interest for applications in light-emitting devices. Herein, the influence of CuO impurities on red-emitting Eu³⁺-doped bismuth borate glasses of the 25Bi₂O₃-15BaO-10Li₂O-50B₂O₃ type was investigated by various spectroscopic methods. The glasses were prepared by the melt-quench technique and characterized by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, UV/Vis optical absorption (OA), and photoluminescence (PL) spectroscopy including decay kinetics assessment. The XRD data confirmed the amorphous nature of the glasses whereas FT-IR spectra indicated the basic structural features of trigonal BO₃ units and BO₄ tetrahedra. The OA analysis showed that addition of CuO up to 0.5 mol% results in significant growth of the visible Cu²⁺ absorption band around 715 nm, with slight decrease in the optical band gap energies assessed through Tauc plots. A drastic PL quenching of Eu³⁺ ions emission was evidenced concurring with the detrimental effect of Cu²⁺. The assessment of the Eu³⁺ emission decay curves revealed significant lifetime decrease of the ⁵D₀ emitting state with increasing CuO concentration. An analysis of quenching constants was finally performed comparing results from integrated PL data with the emission decay rates. It is argued that the bismuth borate glass system supports an effective Eu³⁺→Cu²⁺ energy transfer (more so than phosphates) in connection with a strong spectral overlap between Eu³⁺ emission and Cu²⁺ absorption.     

具有高机械强度的掺Er3+∶TeO2-Nb2O5玻璃的光谱性质研究

熔制了掺铒碲铌玻璃样品(100-XTeO2-XNb2O5(X=5,10,15,20 mol%),测试了其密度、折射率、转变温度、析晶温度、维氏机械强度、吸收光谱、荧光光谱、荧光寿命等参量。利用Judd-Ofelt和McCumber理论分别计算了铒离子强度参量Ωt (t=2, 4, 6)和受激发射截面σemi的大小,研究了掺铒碲铌玻璃样品光谱参量对Nb2O5成分的依赖性,并与典型的碲锌钠玻璃（75TeO2-20ZnO-5Na2O）在热学、机械强度、光谱性质和放大品行四个方面进行了比较.     

Sm3+掺杂稀土硼酸盐玻璃的光谱参数计算和荧光光谱分析

制备了具有高效可见荧光发射的Sm3 掺杂稀土硼酸盐(LBLB)玻璃,对玻璃的吸收和荧光光谱展开了测试与分析.根据Judd-Ofelt理论对吸收光谱进行了拟合,求得Sm3 离子的晶场调节参数Ωt=(2,4,6)分别为6.81×10-20,4.43×10-20和2.58×10-20 cm2,并进一步计算出各能级跃迁的谱线强度、自发辐射跃迁概率、辐射寿命和荧光分支比等光谱参数.紫外光激发下,Sm3 掺杂LBLB玻璃发出明亮的橙红色光.激发光谱表明,氩离子激光器是Sm3 掺杂LBLB玻璃有效的激发光源.     

掺铥氟磷玻璃的结构、热学性质和光谱性质

制备了不同Al(PO3)3含量的掺铥系列氟磷玻璃,研究了其结构、热稳定性和光谱性质。随着Al(PO3)3含量的增加,该系列玻璃的密度降低,折射率增加,差热分析表明,转变温度、析晶起始温度、析晶峰温度和熔化温度增加。Al(PO3)3摩尔浓度在7%~9%时析晶稳定性最佳。采用归一化的拉曼光谱分析了材料的结构和声子状况,对于该系列氟磷玻璃,Al(PO3)3含量的增加不会影响声子能量,但使声子密度增大。测试了样品的吸收光谱,Tm3 的3H6→3F4在第三通信窗口的L波段有明显吸收。与在其它玻璃基质中相比,Tm3 的3F4能级对应能量偏高,3H4能级对应能量偏低,使得3H4→3F4跃迁波长较大,接近于增益迁移光纤放大器的放大波长。扎得奥菲而特(Judd-Ofelt)理论分析表明随着Al(PO3)3含量增加,离子强度参量Ω2增大,Ω6保持相对稳定,Tm3 的能级寿命降低。     

Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃的发光性能

采用传统高温熔融法合成了玻璃组成为B2O3-GeO2-15GdF3-(40-x)Gd2O3-xEu2O3(0≤x≤10)的Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃。在硼锗酸盐玻璃基质中,Gd2O3和GdF3稀土试剂的总含量高达55%,从而确保其密度高于6.4 g/cm^3。闪烁玻璃的光学性能通过光学透过光谱、光致发光光谱、X射线激发发射(XEL)光谱和荧光衰减曲线来表征。玻璃中Gd^3+→Eu^3+离子的能量传递通过激发光谱、发射光谱和Gd^3+-Eu^3+离子间距得到证明,同时也确定了在紫外线和X射线激发下Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃的最佳浓度。Judd-Ofelt理论分析了玻璃中Eu―O键的共价性随Eu^3+掺杂浓度增加而显著增强。Eu^3+激活氟氧硼酸锗酸盐闪烁玻璃在80~470 K温度范围内荧光衰减曲线和发射光谱的温度依赖关系最终证实了其具有较好的发光稳定性。     

一种新型铒镱共掺碲硅酸盐玻璃的光谱性质及荧光俘获效应研究

用高温熔制法制备了系列Er^3＋／Yb^3＋共掺碲硅酸盐玻璃样品，测试和分析了玻璃样品的吸收光谱、荧光光谱、上转换发光光谱及热稳定性。结果表明：这种玻璃具有较宽的荧光半高宽、较大的受激发射截面，较好的热稳定性。970nm泵浦下该系列玻璃在可见光525，546和658nm这3处存在明显的上转换现象，它们分别由Er^3＋离子^2H11/2→^4 I15/2，4S3/2→^4 I15/2和^4 F9/2→^4 I15/2辐射跃迁产生。另外，测试和讨论了在不同样品厚度下玻璃的光谱特性，如荧光光谱、荧光寿命和上转换发光光谱等。结果表明，荧光俘获效应对Er^3＋离子1．5μm波段荧光及上转换发光都有着较大的影响，并随着玻璃厚度的增加而增大，导致测量值与实际值产生较大的偏差。