Zhang Feng, Li Guoqiang, Zhang Weifeng, Yan Yu Li
†School of Physics and Electronics, Henan University, Kaifeng 475004, People's Republic of China.
‡Key Lab of Photovoltaic Materials of Henan Province, Kaifeng 475001, People's Republic of China.
Inorg Chem. 2015 Aug 3;54(15):7325-34. doi: 10.1021/acs.inorgchem.5b00851. Epub 2015 Jul 23.
The phase-dependent upconversion luminescence properties of LaVO4:Er(3+) were studied to provide new insights into the design of new upconversion materials with high efficiency. Er(3+)-, Yb(3+)/Er(3+)-doped t-LaVO4 microcrystals were successfully synthesized by the disodium ethylenediaminetetraacetic acid (Na2EDTA)-assisted hydrothermal method. X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometer (ICP-OES), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, luminescence spectroscopy, and thermogravimetric analysis (TGA) were used to characterize the samples. The results indicated that t-LaVO4 presents sheaf-like morphology, and the possible formation mechanism for these sheaves was proposed on the basis of time-dependent experiments. Furthermore, the phase-dependence (i.e., monoclinic- and tetragonal-type) upconversion luminescence properties were systematically studied, and the upconversion mechanisms were proposed according to spectral, pump power, and the concentration of Yb(3+) dependence analyses. It is worthwhile pointing out that the Er(3+)-doped t-LaVO4 exhibits a brighter green emission, which is approximately 10 times that of m-LaVO4:Er(3+) using a continuous 980 nm laser diode as the excitation source. This remarkable improvement was rationally analyzed on the basis of the composition, crystal structures, Raman spectra, morphology, and size. The comparative experiments suggest that the local structure of Er(3+) was considered as an important reason for the higher fluorescence intensity of t-LaVO4:Er(3+), which was also confirmed by the results of density functional theory (DFT) calculations.
研究了LaVO4:Er(3+)的相依赖上转换发光特性,以便为高效新型上转换材料的设计提供新的见解。通过乙二胺四乙酸二钠(Na2EDTA)辅助水热法成功合成了掺Er(3+)、Yb(3+)/Er(3+)的四方相LaVO4微晶。采用X射线衍射(XRD)、电感耦合等离子体发射光谱仪(ICP-OES)、傅里叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、拉曼光谱、发光光谱和热重分析(TGA)对样品进行了表征。结果表明,四方相LaVO4呈现束状形态,并根据时间相关实验提出了这些束状物可能的形成机制。此外,系统研究了相依赖性(即单斜相和四方相类型)的上转换发光特性,并根据光谱、泵浦功率和Yb(3+)浓度依赖性分析提出了上转换机制。值得指出的是,以连续980 nm激光二极管作为激发源时,掺Er(3+)的四方相LaVO4呈现出更亮的绿色发射,其强度约为单斜相LaVO4:Er(3+)的10倍。基于组成、晶体结构、拉曼光谱、形态和尺寸对这一显著改善进行了合理分析。对比实验表明,Er(3+)的局部结构被认为是四方相LaVO4:Er(3+)荧光强度较高的重要原因,密度泛函理论(DFT)计算结果也证实了这一点。