Effective Space Confinement by Inverse Miniemulsion for the Controlled Synthesis of Undoped and Eu3+-Doped Calcium Molybdate Nanophosphors: A Systematic Comparison with Batch Synthesis

The possibility to precisely control reaction outcomes for pursuing materials with well-defined features is a main endeavor in the development of inorganic materials. Confining reactions within a confined space, such as nanoreactors, is an extremely promising methodology which allows to ensure control over the final properties of the material. An effective room temperature inverse miniemulsion approach for the controlled synthesis of undoped and Eu3+-doped calcium molybdate crystalline nanophosphors was developed. The advantages and the efficiency of confined space in terms of controlling nanoparticle features like size, shape, and functional properties are highlighted by systematically comparing miniemulsion products with calcium molybdate particles obtained without confinement from a typical batch synthesis. A relevant beneficial impact of space confinement by miniemulsion nanodroplets is observed on the control of size and shape of the final nanoparticles, resulting in 12 nm spherical nanoparticles with a narrow size distribution, as compared to the 58 nm irregularly shaped and aggregated particles from the batch approach (assessed by TEM analysis). Further considerable effects of the confined space for the miniemulsion samples are found on the doping effectiveness, leading to a more homogeneous distribution of the Eu3+ ions into the molybdate host matrix, without segregation (assessed by PXRD, XAS, and ICP-MS). These findings are finally related to the photoluminescence properties, which are evidenced to be closely dependent on the Eu(3+ )content for the miniemulsion samples, as an increase of the relative intensity of the direct f-f excitation and a shortening of the lifetime (from 0.901 ms for 1 at. % to 0.625 ms for 7 at. % samples) with increasing Eu3+ content are observed, whereas no relationship between these parameters and the Eu(3+ )content is evidenced for the batch samples. All these results are ascribed to the uniform and controlled crystallization occurring inside each miniemulsion nanodroplet, as opposed to the less controlled nucleation and growth for a classic nonconfined approach.