银改性的空位缺陷发光Cu_(3)I_(4)(Gly)_(3)/Ag的制备及性能研究

Preparation and properties of silver-modified vacancy-defective luminescent Cu_(3)I_(4)(Gly)_(3)/Ag

采用溶剂挥发法合成了银杂化改性的碘铜簇金属有机骨架Cu_(3)I_(4)(Gly)_(3)/Ag。通过傅里叶红外光谱、热重分析谱图、X射线衍射光谱、X光电子能谱、扫描电子显微镜分析和荧光光谱,研究了发光配合物的晶体结构与发光性能。结果表明,引入银形成空位的碘铜簇和甘氨酸构建的发光配合物为四方晶系结构,空间群为F43m。Ag^(+)的引入使得Cu^(+)的电子向Ag^(+)转移形成Ag,产生空位缺陷,增加了缺陷发光中心数量,提高了发光量子效率,同时过多缺陷诱导发光激子产生非辐射复合以及形成更强正电性的Cu^(+)通过甘氨酸配位进行保护,能提高发光配合物的发光效率。当温度从298K升高至403K时,Cu_(3)I_(4)(Gly)_(3)/Ag的荧光强度依然保持初始发光强度的68.56%。其色坐标位于(0.5357,0.3576)的橙红色区域,量子效率为1.95%,具有出色的发光性能和良好的热稳定性能,是一种应用前景广泛的新型发光防伪材料。

The metal-organic backbone Cu_(3)I_(4)(Gly)_(3)/Ag modified by silver hybridization was synthesized by solvent volatilization method.The crystal structure and luminescence properties of the luminescent complexes were investigated by Fourier infrared spectroscopy,thermogravimetric analysis spectroscopy,X-ray diffraction spectroscopy,X-ray electron spectroscopy,scanning electron microscopy analysis and fluorescence spectroscopy.The results show that the luminescent complexes constructed by introducing silver to form vacancies of iodinecopper clusters and glycine have a tetragonal crystal structure with a space group of F43m.The introduction of Ag*makes the electron transfer from Cu^(+)to Ag^(+)to form Ag and provide vacancies,which increases the number of defective luminescent centers and improves the luminescence quantum efficiency,while too many defects induce non-radiative omplexation of luminescent excitons and electron transfer to form stronger.The presence of positively charged Cu*also leads to a decrease in the stability of the luminescent material,which is further protected by glycine coordination and can improve the luminescence efficiency of the luminescent complexes.When the temperature was increased from 298K to 403K,the fluorescence intensity of Cu_(3)I_(4)(Gly)_(3)/Ag remained 68.56%of the initial luminescence intensity.Its color coordinates are located in the orange-red region of(0.5357,0.3576),and its quantum efficiency is 1.95%.It has excellent luminescence performance and good thermal stability,and is a new luminescent anti-counterfeiting material with wide application prospects.