SiO2对掺钕铝酸盐玻璃结构及光谱性质的影响

doi:10.15541/jim20150189

摘要/Abstract

摘要：

实验通过高温熔融法制备了不同SiO₂浓度的掺钕钙铝酸盐玻璃。采用拉曼光谱法分析玻璃结构变化, 发现随着SiO₂含量的增加, [AlO₄]网格中非桥氧逐渐转移至Si⁴⁺离子周围, 玻璃主体Al-O网络中非桥氧减少, 聚合度提高。实验测试了玻璃的吸收光谱和荧光光谱, 并运用Judd-Ofelt理论计算Nd³⁺离子⁴F_3/2→⁴I_11/2跃迁的J-O参数Ω, 自发辐射几率A_rad, 荧光分支比β, 受激发射截面σ_e, 辐射寿命τ_rad等。结果显示: 随着SiO₂浓度的增加, 钕离子周围环境结构对称性提高, 荧光发射峰半高宽变窄, 同时受激发射截面逐渐增大。研究结果表明含有低浓度SiO₂的掺钕钙铝酸盐激光玻璃有望用于超短脉冲激光领域。

关键词: 光谱, 钙铝酸盐玻璃, 钕掺杂, 结构变化, 荧光半高宽

Abstract:

Nd³⁺-doped calcium-aluminate glasses with different contents of SiO₂were prepared by conventional melting method. The change of glasses structures were studied by Raman spectroscope. The non-bridging oxygens (NBOs) around Si⁴⁺ ions increase at higher SiO₂ content samples which are transferred from alumina tetrahedron lattices and a more polymerization Al-O network appears in glass structure due to lower NBOs content. From the absorption spectra, J-O strength parameters (Ω), spontaneous transition probabilities (A_rad), branching ratios (β), emission cross-sections (σ_e), and radiative life (τ_rad) were evaluated by Judd-Ofelt theory. Analysis on the evaluation result and fluorescence spectra reveal that the surrounding structure symmetry of Nd³⁺ ions is ameliorated and the full width at half maximum (FWHM) of emission peak at 1067 nm is narrowed, meanwhile the emission cross-sections is enlarged gradually with the SiO₂ content increasing. These results show that Nd³⁺-doped calcium aluminate glass containing low content of SiO₂ has potential applications in ultrashort-pulse laser materials.

Key words: spectroscopy, calcium aluminosilicate glass, neodymium doped, glass structure, FWHM

中图分类号:

TQ174

康帅, 何冬兵, 高松, 黄飞飞, 丁亚军, 胡丽丽. SiO₂对掺钕铝酸盐玻璃结构及光谱性质的影响[J]. 无机材料学报, 2015, 30(11): 1177-1182.

KANG Shuai, HE Dong-Bing, GAO Song, HUANG Fei-Fei, DING Ya-Jun, HU Li-Li. Effects of Silicon Dioxide on Structure and Spectroscopic Properties of Neodymium Doped Calcium Aluminate Glass[J]. Journal of Inorganic Materials, 2015, 30(11): 1177-1182.

图/表 9

图1 七种钙铝酸盐钕玻璃的差示扫描量热分析曲线

Fig. 1 DSC curves of Nd3+-doped CA glasses with the different concentrations of SiO2

表1 钙铝酸盐钕玻璃的主要物理性质参数

Table 1 Main physical parameters of Nd3+-doped CA glasses

Sample	S0	S2	S4	S6	S8	S10	S12
T_g/℃	809	816	810	827	823	842	848
T_x/℃	924	929	927	931	938	945	963
ΔT/℃	115	113	117	104	115	103	115
K_gl	0.175	0.174	0.179	0.161	0.179	0.162	0.186
n_d	1.6749	1.672	1.6692	1.6652	1.6619	1.6593	1.6554
ρ/(g•cm^-3)	3.33	3.34	3.33	3.31	3.32	3.29	3.29

图2 七种钙铝酸盐钕玻璃的归一化拉曼光谱

Fig. 2 Normalized Raman spectra for Nd3+-doped CA glasses with the different concentrations of SiO2

图3 Nd3+在样品S0中的吸收光谱

Fig. 3 Absorption spectra of Nd3+-doped CA glass without SiO2

图4 Nd3+的主要能级结构图

Fig. 4 Partial energy level diagram for Nd3+

表2 钙铝酸盐玻璃中Nd3+的J-O参数Ωλ(λ=2,4,6)/(×10-20, cm-2)、自发辐射几率Arad/s-1和荧光分支比β

Table 2 J-O strength parameters Ωλ(λ=2,4,6)/(×10-20, cm-2), spontaneous transition probability Arad/s-1 and branching ratios β of Nd3+ in CA glasses

Sample	Ω₂	Ω₄	Ω₆	A(⁴F_3/2→⁴I_11/2)	Β(⁴F_3/2)
S0	5.69	4.82	3.61	1361	0.46
S2	5.63	4.87	3.53	1369	0.463
S4	5.69	4.87	3.69	1387	0.464
S6	5.45	4.79	3.66	1361	0.465
S8	5.36	4.75	3.72	1364	0.467
S10	5.33	4.83	3.83	1391	0.468
S12	5.13	4.82	3.8	1372	0.468

图5 钙铝酸盐钕玻璃4F3/2→4I11/2的受激发射截面随SiO2浓度变化的关系

Fig. 5 Emission cross section of Nd3+:4F3/2→4I11/2 in CA glasses

表3 不同基质玻璃的Nd3+的荧光带宽FWMH、荧光中心波长λ、辐射寿命τrad和发射截面σe

Table 3 Florescence bandwidth FWMH, radiative life τrad, peak-fluorescence wavelength λ and emission cross section σe of Nd3+ for different host glasses

Sample	S0	S2	S4	S6	S8	S10	S12	N31	Q-246	L-65
FWHM	39.70	38.80	37.90	38.00	37.10	36.50	36.30	20.10	28.50	41.23
λ/nm	1067	1067	1067	1066	1066	1066	1065	1053	1061	1067
τ_rad/μs	338	338	335	342	343	337	341	351	406	349
σ_e/(×10^-20, cm²)	1.84	1.85	1.90	1.92	1.92	2.04	2.02	3.80	2.40	1.80

图6 七种玻璃中Nd3+离子的归一化荧光光谱

Fig. 6 Normalized fluorescence spectra for Nd3+-doped CA glasses with the different content of SiO2

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SiO₂对掺钕铝酸盐玻璃结构及光谱性质的影响

Effects of Silicon Dioxide on Structure and Spectroscopic Properties of Neodymium Doped Calcium Aluminate Glass

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