Tuning the dielectric response in a nanocomposite material through nanoparticle morphology

Ceramic materials such as metal oxides, mixed metal oxides and silicates, constitute a broadly-used, high-performance technology for electronic insulators. The introduction of metal cluster dopants and molecular-scale inclusions in a dielectric matrix provides an opportunity for manufacturing new high-κ solid-state dielectrics with tunable field-response properties. The quantum properties of these metallic nanoparticles depend strongly on their size and shape, a characteristic that can be exploited in changing the response properties of a material, whereas the small nanoparticle size can help limit the issues of conduction and current leakage. Here, we model the polarization of molecular-scale silver inclusions in a magnesium oxide matrix, using the Modern Theory of Polarization and Car-Parrinello Molecular Dynamics (CPMD). Details of the implementation are laid out, including handling of current jumps due to the distortion of the matrix during the simulation. Several trends in the dielectric response are considered in this work, including the effects of nanoparticle size, shape and orientation relative to the applied field. Dielectric permittivity enhancements of 30-100% are observed with inclusion sizes varying from 8 to 32 atoms, considering both rod-like and disk-like inclusions, with alignment either parallel or perpendicular to the external field.