离子交换和热处理对贵金属掺杂硅酸盐玻璃光致发光的影响

doi:10.15541/jim20160214

摘要/Abstract

摘要：

贵金属纳米颗粒-玻璃复合材料是一种重要的非线性材料。利用光致发光谱及配位场理论, 深入研究了离子交换及氢气热处理对硅酸盐玻璃中贵金属离子的引入、还原、成核及生长过程的影响, 发现延长离子交换时间有利于提高玻璃中金属离子的浓度。对于掺Ag⁺硅酸盐玻璃, 不仅存在孤立Ag⁺离子, 同时也存在Ag₂⁺团簇。H₂中热处理后, 样品中孤立Ag⁺离子浓度迅速降低, 同时出现Ag₃²⁺团簇。对于掺Cu⁺硅酸盐玻璃, 仅存在孤立Cu⁺和Cu²⁺, 没有发现Cu⁺团簇的发光峰, Cu²⁺的存在造成Cu⁺的发光强度显著降低。掺Ag⁺硅酸盐玻璃经H₂热处理后, 再经过第二次离子交换往玻璃中掺Cu⁺是十分困难的。

关键词: 离子交换, 热处理, 贵金属离子及团簇, 光致发光, 配位场理论

Abstract:

Noble metallic nanoparticles-glass composites have attracted much interest because of their technical potential as nonlinear media. In present work, the influences of ion-exchange and thermal treatment on the photoluminescence of noble metal doped silicate glasses were discussed based on photoluminescence (PL) spectroscopy and ligand field theory. The results indicate that metallic ion concentration in silicate glass increases with extending ion-exchanged period. There exist isolated Ag⁺ ions and Ag₂⁺ clusters in Ag-doped silicate glass. Concentration of the isolated Ag⁺ ions decreases quickly and Ag₃²⁺ clusters appear after annealing the Ag-doped silicate glass in H₂. While there exist only isolated Cu⁺ and Cu²⁺ ions in the Cu-doped silicate glass, no photoluminescence of Cu⁺ clusters are found in the glass. The existence of Cu²⁺ ions makes the luminescence of Cu⁺ quenching. It is very difficult to introduce Cu⁺ ions into the annealed Ag-doped glass in H₂ via Cu⁺ for Na⁺ ion-exchange.

Key words: ion-exchange, thermal treatment, nobel metallic ions and clusters, photoluminescence, ligand field theory

中图分类号:

TQ174

杨修春. 离子交换和热处理对贵金属掺杂硅酸盐玻璃光致发光的影响[J]. 无机材料学报, 2016, 31(10): 1039-1045.

YANG Xiu-Chun. Influences of Ion Exchange and Thermal Treatment on Photoluminescence of Noble Metal Doped Silicate Glasses[J]. Journal of Inorganic Materials, 2016, 31(10): 1039-1045.

图/表 7

图1 离子交换时间(a)和离子交换温度(b)对样品光致发光的影响

Fig. 1 Influences of ion-exchanged period (a) and temperature (b) on photoluminescence of Cu-doped silicate glasses PL spectra excited by 280 nm and PLE spectra detected by 500 nm

图2 玻璃中Cu+的八面体配位场能级图[26]

Fig. 2 Level configuration scheme for the Cu+ ion, with the effect of a tetragonal distortion of the octahedral field[26]

图3 在280 nm激发光下样品Cu-H-1和Cu-H-2的光致发光谱

Fig. 3 PL spectra of samples Cu-H-1 and Cu-H-2 excited by 280 nm

图4 (a)在240 nm激发波长下掺Ag钠钙硅酸盐玻璃的发光谱, (b)Ag-1发光谱减去硅酸盐玻璃基体的发光谱, 点线为高斯拟合

Fig. 4 (a) PL spectra of Ag-doped silicate glasses excited by 240 nm and a representative excitation spectrum detected by 360 nm emission; (b) PL differential spectrum of sample Ag-1 subtracting sodalime silicate glass (solid line) and the corresponding Gaussian fits (dot lines)

图5 AgNO3质量分数对掺Ag硅酸盐玻璃光致发光的影响

Fig. 5 Influences of AgNO3 mass fraction on photoluminescence of Ag-doped silicate glasses at excitation wavelength of 240 nm

图6 样品Ag-2和Ag-6的发光谱和发射谱

Fig. 6 PL and PLE spectra of samples Ag-2 and Ag-6 (a) PL spectra excited by 240 nm; (b-d) PLE spectra of Ag-6 detected by 345 nm, 510 nm and 670 nm, respectively

图7 样品Ag-Cu-1和Ag-Cu-2的发光谱和激发谱

Fig. 7 PL and PLE spectra of samples Ag-Cu-1 and Ag-Cu-2 (a) PL spectra excited by 240 nm (b) PLE spectra of sample Ag-Cu-1 detected by 550 nm (dash curve) and 640 nm (dot curve), respectively

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