Luminescent calcium carbonate micro ‘bow ties’

Calcium carbonate (CaCO3) is a ubiquitous material which has been studied for centuries due to its integral nature across various fields and its vast range of applications. Here we report, for the first time, a low temperature dry ice carbonation method for the production of unique rare earth-doped calcium carbonate ‘bow ties’. CaCO3 exhibits retrograde solubility, an interesting property in which its solubility increases with decreasing temperature. In this synthesis, dry ice acts not only as a CO2 source, but as a coolant, increasing the solubility of CaCO3 and CO2 and allowing specific growth to occur. The incorporation of trivalent lanthanide ions Eu3+ and Tb3+ into the CaCO3 synthesis results in the formation of these unique luminescent calcite ‘bow tie’ microstructures which cannot be produced using either standard gaseous CO2 carbonation, or chemical precipitation methods. This new method and materials might find potential applications including, but not limited to, radionuclide sequestration, imaging and photonics.