Lanthanide-doped nanocrystals: synthesis, optical-magnetic properties, and applications

Acc Chem Res. 2011 May 17;44(5):322-32. doi: 10.1021/ar100129p. Epub 2011 Mar 11.


Because of the potential applications of lanthanide-doped nanocrystals in display devices, optical communication, solid-state lasers, catalysis, and biological labeling, the controlled synthesis of these new nanomaterials has sparked considerable interest. Nanosized phosphorescent or optoelectronic devices usually exhibit novel properties, depending on their structures, shapes, and sizes, such as tunable wavelengths, rapid responses, and high efficiencies. Thus, the development of facile synthetic methods towards high-quality lanthanide-doped nanocrystals with uniform size and shape appears to be of key importance both for the exploration of their materials properties and for potential applications. This Account focuses on the recent development in our laboratory of the synthesis and applications of lanthanide-doped nanocrystals. Since 2005, when we proposed a general strategy for nanocrystal synthesis via a liquid-solid-solution process, a range of monodisperse and colloidal lanthanide-doped fluoride, oxide, hydroxide, orthovanadate, thiooxide, borate, and phosphate nanocrystals have been successfully prepared. By rationally tuning the reaction conditions, we have readily synthesized nanostructures, such as hollow microspheres, nanorods, nanowires, hexagonal nanoplates, and nanobelts. By adjusting the different colloidal nanocrystal mixtures, we fabricated unique binary nanostructures with novel dual-mode luminescence properties through a facile ultrasonic method. By tridoping with lanthanide ions that had different electronic structures, we successfully achieved β-NaYF(4) nanorods that were paramagnetic with tuned upconversion luminescence. We have also used NaYF(4):Yb(3+)/Er(3+) conbined with magnetite nanoparticles as a sensitive detection system for DNA: NaYF(4):Yb(3+)/Er(3+) and Fe(3)O(4) nanoparticles were modified with two different DNA sequences. Then, the modified NaYF(4):Yb(3+)/Er(3+) nanoparticles were conjugated to the modified Fe(3)O(4) nanoparticles. These binary nanoparticles can be hybridized with a third DNA (target DNA) molecule and separated with the assistance of a magnetic field. In addition, a novel fluorescence resonance energy transfer (FRET) method for nonenzymatic glucose determination has been developed by using the glucose-modified LaF(3):Ce(3+)/Tb(3+) nanocrystals. By using bioconjugated NaYF(4):Yb(3+)/Er(3+) nanoparticles as the energy donor and bioconjugated gold nanoparticles as the energy acceptor, we successfully developed a simple and sensitive fluorescence resonance energy transfer (FRET) biosensor for avidin. Meanwhile, we also carried out preliminary studies to investigate possible applications of lanthanide-doped nanocrystals in catalysis and in dye-sensitized solar cells.