Colossal permittivity in advanced functional heterogeneous materials: the relevance of the local measurements at submicron scale

Recently, giant dielectric permittivities (? ? ~ 104) have been found in several nonferroelectric materials such as CaCu3Ti4O12 (CCTO) (Subramanian et al., J. Solid State Chem. 151:323, 2000; Homes et al., Science 293:673, 2001), doped-NiO (Wu et al., Phys. Rev. Lett. 89:217601, 2002) systems (Li x Ti y Ni1 - x - y O, Li x Si y Ni1 - x - y O, Ki x Ti y Ni1 - x - y O), CuO, (Lin et al., Phys. Rev. B 72:014103, 2005; Sarkar et al., App. Phys. Lett. 92:142901, 2008) etc., and most important, the high ? ? values of these materials are almost independent over a wide range of temperature. This is one of the most intriguing features for their implementations in microelectronics devices, and as a consequence, these materials have been subjected to extensive research. Here, an introduction to such materials and to the methods for their dielectric characterization is given. So far, the crucial question is whether the large dielectric response is an intrinsic property of new class of crystals or an extrinsic property originated by a combination of the structural properties and other features such as defects and inhomogeneities. Preliminary, this peculiar dielectric behavior has been explained in powder ceramics by the internal barrier layer capacitor (IBLC) model, that is the presence of semiconducting domains surrounded by thin insulating regions within the crystal microstructure. It has been considered the most appropriate model and it has been generally accepted to explain the giant response of these materials. However, it could not be transferred to single crystals and thin films. In this scenario, scanning probe-based methods (like STM, KPFM, C-AFM, SIM etc) represent the most powerful instrument to understand the colossal permittivity-related physical phenomena, by investigations at nanoscale, clarifying the local effects responsible of the rising of macroscopic giant dielectric responses. Scanning probe microscopy investigations showed the relevance of inhomogeneity within single crystal, polycrystalline ceramics, and thin films. In particular, they are powerful tools to point out the presence of few nanometer wide internal barrier layers and of electrical domains, which are not recognisable with standard macroscopic electric characterization techniques.