Quantum-sized ZnS nanocrystals with quasi-spherical and rod shapes were synthesized by the aging reaction mixtures containing diethylzinc, sulfur, and amine. Uniform-sized ZnS nanorods with the average dimension of 5 nm x 21 nm, along with a small fraction of 5 nm-sized quasi-spherical nanocrystals, were synthesized by adding diethylzinc to a solution containing sulfur and hexadecylamine at 125 degrees C, followed by aging at 300 degrees C. Subsequent secondary aging of the nanocrystals in oleylamine at 60 degrees C for 24 h produced nearly pure nanorods. Structural characterizations showed that these nanorods had a cubic zinc blende structure, whereas the fabrication of nanorods with this structure has been known to be difficult to achieve via colloidal chemical synthetic routes. High-resolution TEM images and reaction studies demonstrated that these nanorods are formed from the oriented attachment of quasi-spherical nanocrystals. Monodisperse 5 nm-sized quasi-spherical ZnS nanocrystals were separately synthesized by adding diethylzinc to sulfur dissolved in a mixture of hexadecylamine and 1-octadecene at 45 degrees C, followed by aging at 300 degrees C. When oleic acid was substituted for hexadecylamine and all other procedures were unchanged, we obtained 10 nm-sized quasi-spherical ZnS nanocrystals, but with broad particle size distribution. These two different-sized quasi-spherical ZnS nanocrystals showed different proportions of zinc blende and wurtzite crystal structures. The UV absorption spectra and photoluminescence excitation spectra of the 5 nm ZnS quasi-spherical nanocrystals and of the nanorods showed a blue-shift from the bulk band-gap, thus showing a quantum confinement effect. The photoluminescence spectra of the ZnS nanorods and quasi-spherical nanocrystals showed a well-defined excitonic emission feature and size- and shape-dependent quantum confinement effects.
Core/shell upconverting nanoparticles (UCNPs) of NaGdF4:Er3+,Yb3+/NaGdF4 (see figure) are shown to serve as a multimodal imaging probe that works for both background‐free optical imaging and magnetic resonance imaging (MRI). The nonblinking and nonbleaching properties of UCNPs can contribute to minimization of possible artifacts in long‐term imaging experiments. Owing to Gd3+ ions in the host matrix, contrast is enhanced in T1‐weighted MRI.
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