Millimeter-Sized K2MnF6:Si4+, NH4+ Red-Luminescent Crystals with High Absorption Efficiency (AEmax of 93.5%) and External Quantum Efficiency (EQEmax of 68.9%) Grown by Cooling-Induced Crystallization.

Luminescent bulk crystals exhibit fewer grain boundaries and defects compared with conventional microsized powdery ones. Herein, targeting Mn4+-activated fluoride crystals with a sharp line-type red luminescence spectrum, we propose a new cooling-induced crystallization method to grow the fluoride crystals. By this new method, we successfully grew millimeter-sized K2MnF6:Si4+, NH4+ crystals, featuring an AEmax (absorption efficiency) of 93.5% and an EQEmax (external quantum efficiency) of 68.9%, which are among the best values for Mn4+-activated fluoride red phosphors. The influence of doping Si4+ and/or NH4+ in K2MnF6 on the local coordination structure and luminescence properties was studied. The anomalous thermal quenching behaviors were discussed, the luminescence decay from the excited state was compared, and the origin for the high quantum efficiencies was analyzed.

Ion diffusion retarded by diverging chemical susceptibility.

For first-order phase transitions, the second derivatives of Gibbs free energy (specific heat and compressibility) diverge at the transition point, resulting in an effect known as super-elasticity along the pressure axis, or super-thermicity along the temperature axis. Here we report a chemical analogy of these singularity effects along the atomic doping axis, where the second derivative of Gibbs free energy (chemical susceptibility) diverges at the transition point, leading to an anomalously high energy barrier for dopant diffusion in co-existing phases, an effect we coin as super-susceptibility. The effect is realized in hydrogen diffusion in vanadium dioxide (VO2) with a metal-insulator transition (MIT). We show that hydrogen faces three times higher energy barrier and over one order of magnitude lower diffusivity when it diffuses across a metal-insulator domain wall in VO2. The additional energy barrier is attributed to a volumetric energy penalty that the diffusers need to pay for the reduction of latent heat. The super-susceptibility and resultant retarded atomic diffusion are expected to exist universally in all phase transformations where the transformation temperature is coupled to chemical composition, and inspires new ways to engineer dopant diffusion in phase-coexisting material systems.