Okram Reena, Yaiphaba Ningombam, Ningthoujam Raghumani Singh, Singh Nongmaithem Rajmuhon
Department of Chemistry, Manipur University , Imphal-795003, India.
Inorg Chem. 2014 Jul 21;53(14):7204-13. doi: 10.1021/ic500828s. Epub 2014 Jun 25.
Crystalline LaVO4:Eu(3+) nanophosphors (NPs) codoped with metal ions (M(n+) = Li(+), Sr(2+), and Bi(3+)) are prepared in ethylene glycol (EG) medium at temperature ∼140 °C in 3 h. A mixture of monoclinic and tetragonal phases is observed. The ratio of tetragonal to monoclinic phases increases with increase of Li(+) and Sr(2+) concentration, but this is opposite in case of Bi(3+) concentration. Lattice expansion occurs in the case of Li(+) and Sr(2+) codoping. Li(+) ions occupy the interstitial sites instead of La(3+) sites. Lattice contraction occurs in case of Bi(3+) codoping indicating substitution of La(3+) sites. Luminescence intensity is improved by codoping of M(n+) irrespective of crystal structure. Charges of Li(+) and Sr(2+) are different from that of La(3+) (host lattice), whereas the charge of Bi(3+) is same as that of La(3+). One interesting observation is in magnetic dipole transition that the intensity of the peak at 594 nm is more than that at 587 nm in the case of charge imbalance, whereas the reverse occurs in the case of charge balance. LaVO4:Eu(3+) nanophosphors prepared in water medium have more luminescence intensity when compared to those prepared in ethylene glycol, and this is related to variation of ratio of tetragonal to monoclinic phases. The luminescence intensity is also enhanced as annealing temperature increases from 600 to 800 °C due to the improved crystallinity. Lifetime data are analyzed on the basis of exponential and nonexponential decay equations. Samples are dispersible in polar medium due to capping of particles by EG. Polymer films are prepared by dispersion of NPs in poly(vinyl alcohol), and extra borax is added in order to make cross-link between polymer molecules. Samples of NPs in the forms of powder, dispersion in liquid medium, and film show the red emission.
在乙二醇(EG)介质中于约140℃温度下3小时内制备了共掺杂金属离子(Mⁿ⁺ = Li⁺、Sr²⁺和Bi³⁺)的结晶LaVO₄:Eu(3+)纳米磷光体(NPs)。观察到单斜相和四方相的混合物。四方相与单斜相的比例随Li⁺和Sr²⁺浓度的增加而增加,但在Bi³⁺浓度的情况下则相反。Li⁺和Sr²⁺共掺杂时发生晶格膨胀。Li⁺离子占据间隙位置而非La³⁺位置。Bi³⁺共掺杂时发生晶格收缩,表明La³⁺位置被取代。无论晶体结构如何,Mⁿ⁺的共掺杂都会提高发光强度。Li⁺和Sr²⁺的电荷与La³⁺(主体晶格)不同,而Bi³⁺的电荷与La³⁺相同。一个有趣的观察结果是在磁偶极跃迁中,在电荷不平衡的情况下,594 nm处峰的强度大于587 nm处的强度,而在电荷平衡的情况下则相反。与在乙二醇中制备的相比,在水介质中制备的LaVO₄:Eu(3+)纳米磷光体具有更高的发光强度,这与四方相与单斜相的比例变化有关。由于结晶度提高,当退火温度从600℃升高到800℃时,发光强度也会增强。基于指数和非指数衰减方程分析寿命数据。由于EG对颗粒的包覆作用,样品可分散在极性介质中。通过将NPs分散在聚乙烯醇中来制备聚合物薄膜,并添加额外的硼砂以使聚合物分子之间交联。粉末、液体介质中的分散体和薄膜形式的NPs样品均呈现红色发射。