Research Center for Light Emitting Diodes (LED), Zhejiang Normal University, Jinhua 321004, PR China.
J Colloid Interface Sci. 2011 Jun 15;358(2):334-7. doi: 10.1016/j.jcis.2011.03.036. Epub 2011 Mar 15.
ZnO:Er(3+) and ZnO:Er(3+)-Yb(3+) nanoparticles (NPs) are fabricated by a sol-gel method, afterwards parts of which are separated and surface modified in Mo(NO(3))(3) solution. Analyses on phase and structure based on X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) techniques indicate that Er(3+) and Yb(3+) are incorporated into the ZnO lattice successfully and after Mo treatment, a thin layer of MoO(3) forms on the NPs surface, forming core/shell structures. Raman scattering spectra reveal the existence of ZnMoO(4) in the shell part. Visible up-conversion (UC) is observed in all the samples, with Mo treated and untreated ZnO:Er(3+) emitting dominant but relatively weak red light, corresponding to (4)F(9/2)-(4)I(15/2) transition of Er(3+). In Yb(3+)-codoping systems, the integral UC intensity is enhanced obviously though red emission still dominates the UC spectra before surface modification. In the Mo treated system, ZnO:Er(3+)-Yb(3+)/MoO(3), green emission is increased while the red is suppressed in comparison to ZnO:Er(3+)-Yb(3+), with the intensity of green to red ratio (GRR) changing from 0.25 to 8. A novel phenomenon is discovered that the green emissions in our samples involve three-photon processes.
采用溶胶-凝胶法制备了 ZnO:Er(3+)和 ZnO:Er(3+)-Yb(3+)纳米粒子(NPs),部分 NPs 经分离后用 Mo(NO(3))(3)溶液进行表面修饰。基于 X 射线衍射(XRD)和高分辨率透射电子显微镜(HRTEM)技术的相和结构分析表明,Er(3+)和 Yb(3+)成功掺入 ZnO 晶格中,经 Mo 处理后,NPs 表面形成一层 MoO(3),形成核/壳结构。拉曼散射光谱表明壳层部分存在 ZnMoO(4)。所有样品均观察到可见上转换(UC),未经处理和经 Mo 处理的 ZnO:Er(3+)均发射较强的但相对较弱的红光,对应于 Er(3+)的 (4)F(9/2)-(4)I(15/2)跃迁。在 Yb(3+)共掺杂体系中,尽管在表面修饰之前,红色发射仍然主导 UC 光谱,但整体 UC 强度明显增强。在 Mo 处理体系中,与 ZnO:Er(3+)-Yb(3+)相比,ZnO:Er(3+)-Yb(3+)/MoO(3)的绿光发射增强,红光发射受到抑制,绿光到红光的强度比(GRR)从 0.25 变为 8。我们发现了一个新现象,即我们样品中的绿光发射涉及三光子过程。