Ultrathin Ca-PO4-CO3 Solid-Solution Nanowires: A Controllable Synthesis and Full-Color Emission by Rare-Earth Doping

It was found that calcium carbonate (CaCO3) and hydroxyapatite (Ca10(OH)2(PO4)6), which are two crucial constituents of the most abundant minerals in nature and very important bioinorganic components in the tissues of mineralizing organisms, can form solid solutions in a wide range of PO43-/CO32- (P/C) ratios at low temperature when prepared as ultrathin nanowire structures. This is due to the special reactivity of ultrasmall nanocrystals, which can effectively lower the synthetic temperature and promote the formation of solid solutions. The as-prepared ultrathin nanowires with suitable P/C ratios presented strong blue luminescence due to the existence of abundant defects strengthened by CO32-. If used as the matrix, the as-prepared ultrathin nanowires demonstrated bright green or red luminescent properties when doped with Tb3+ or Eu3+ ions, and simultaneously retained their original morphologies. These three kinds of fluorescent nanowires could reproduce a full range of luminescence colors based on additive color mixtures of the three primary colors (red, green, and blue). In addition, under the same reaction system, ultrafine rare-earth-doped (Ce3+, Tb3+, Eu3+) nanowires (about 1 nm in diameter) were synthesized by using a one-step hydrothermal process, which further pushed the size of the Ca-PO4-CO3 nanobuilding blocks to one unit cell region. These ultrafine nanowires displayed excellent film-forming properties and the ability to absorb UV radiation.