High T c layered ferrielectric crystals by coherent spinodal decomposition
Research in the rapidly-developing field of 2D-electronic materials has thus far been focused on metallic and semiconducting materials. However, complementary dielectric materials such as non-linear dielectrics are needed to enable realistic device architectures. Candidate materials require tunable dielectric properties and pathways for heterostructure assembly. Here we report on a family of cation-deficient transition metal thiophosphates whose unique chemistry makes them a viable prospect for these applications. In these materials, naturally occurring ferrielectric heterostructures composed of centrosymmetric In 4/3 P 2 S 6 and ferrielectrically-active CuInP 2 S 6 are realized by controllable chemical phase separation in van-der-Waals bonded single crystals. CuInP 2 S 6 by itself is a layered ferrielectric with Tc just over room-temperature which rapidly decreases with homogenous doping. Surprisingly, in our composite materials, the ferrielectric Tc of the polar CuInP 2 S 6 phase increases. This effect is enabled by unique spinodal decomposition that retains the overall van-der-Waals layered morphology of the crystal, but chemically separates CuInP 2 S 6 and In 4/3 P 2 S 6 within each layer. The average spatial periodicity of the distinct chemical phases can be finely controlled by altering the composition and/or synthesis conditions. One intriguing prospect for such layered spinodal alloys is large volume synthesis of 2D in-plane heterostructures with periodically alternating polar and non-polar phases.