Increased NIR photoluminescence of Egyptian blue via matrix effect optimization

Abstract

The exceptionally high NIR photoluminescence of the ancient pigment Egyptian blue is due to its very stable phase cuprorivaite (CaCuSi4O10). This compound has recently attracted significant attention, leading to numerous applications for sensors, luminescent solar concentrators, energy-saving, and biomedicine. Here we report an innovative manufacturing process for producing high-grade cuprorivaite, characterized by fine crystal grains and a significantly increased NIR photoluminescence emission. The unprecedented ultra-high NIR emission (quantum yield ΦEM ≈ 30 %) is almost three times higher than the best one reported so far. This is an important turning point for the extension of applications of cuprorivaite to new sectors and can greatly boost its exploitation. The new high-efficiency cuprorivaite is obtained by solid-state synthesis, using silica nanoparticles as a starting material and avoiding fluxing agents. No doping with rare-earths or other elements has been employed, making synthesis straightforward and sustainable. The material obtained has been fully characterized in terms of crystalline, morphological, and optical properties and compared to cuprorivaite obtained through traditional melt-flux synthesis. The main difference observed is that the tiny crystals obtained through the new synthesis method are practically devoid of the glassy phase, rich in copper and impurities, that is instead largely present in Egyptian Blue pigment synthesized with traditional melt-flux synthesis. We speculate that this glassy phase is responsible for the partial suppression of the intrinsic photoluminescence of cuprorivaite, demonstrating how limiting the glassy phase can increase the external quantum efficiency of Egyptian blue.