Synthesis, Luminescence and Energy Transfer Properties of Ce3+/Mn2+ Co-Doped Calcium Carbodiimide Phosphors

Abstract

Ce3+-doped and Ce3+/Mn2+ co-doped calcium carbodiimide (CaCN2) phosphors were synthesized from doped calcium carbonate and carbon nitride by a solid-state reaction at 700 °C under flowing NH3 using a very short reaction time (1 h). The samples were characterized by powder X-ray diffraction, scanning electron microscopy and their diffuse reflectance and luminescence properties were investigated. Single-doped CaCN2:Ce3+ exhibits a blue emission under near-ultraviolet activation (386 nm) corresponding to the 5d1 → 2F5/2 and 5d1 → 2F7/2 transitions of Ce3+. Maximum emission is obtained at temperatures lower than 150 K and then progressively decreases up to 387 K, with an 80% drop in the emission at room temperature. Efficient energy transfers from Ce3+ to Mn2+ via a non-radiative dipole–dipole mechanism are evidenced for the co-doped samples, leading to various colored phosphors under near-ultraviolet activation (386 nm). The emission color of the obtained phosphors can be modulated from blue to red through a shade of white depending on the sensitizer/activator ratio.

The [NCN]2– Carbodiimide Complex Anion and Its Compounds–A “Divalent Nitride” Unit for Nitridocarbonates in Materials and Applications

“…Calcium carbodiimide has been partially substituted with trivalent cerium ions, i.e., CaNCN:Ce 3+ and codoped with Mn 2+ , i.e., CaNCN:Ce 3+ /Mn 2+ . 120 CaNCN:Ce 3+ exhibits blue emission. For codoped CaNCN:Ce 3+ /Mn 2+ the emission color can effectively be tuned by changing the sensitizer:activator ratio.…”

“…Calcium carbodiimide has been partially substituted with trivalent cerium ions, i.e., CaNCN:Ce 3+ and codoped with Mn 2+ , i.e., CaNCN:Ce 3+ /Mn 2+ . CaNCN:Ce 3+ exhibits blue emission.…”