Non-intrinsic origin of the Colossal Dielectric Constants in CaCu3Ti4O12

The dielectric properties of CaCu3Ti4O12, a material showing colossal values of the dielectric constant, were investigated in a broad temperature and frequency range extending up to 1.3 GHz. A detailed equivalent circuit analysis of the results and two crucial experiments, employing different types of contacts and varying sample thickness, provide clear evidence that the apparently high values of the dielectric constant in CaCu3Ti4O12 are non-intrinsic and due to electrode polarization effects. The intrinsic properties of CaCu3Ti4O12 are characterized by charge transport via hopping of localized charge carriers and a relatively high dielectric constant of the order of 100.Comment: 4 pages, 4 figure

Channel diffusion of sodium in a silicate glass

We use classical molecular dynamics simulations to study the dynamics of sodium atoms in amorphous Na$_2$O-4SiO$_2$. We find that the sodium trajectories form a well connected network of pockets and channels. Inside these channels the motion of the atoms is not cooperative but rather given by independent thermally activated hops of individual atoms between the pockets. By determining the probability that an atom returns to a given starting site, we show that such events are not important for the dynamics of this system.Comment: 10 pages of Latex, 5 figures, one figure added, text expande

Origin of Low-Energy Excitations in Charge-Ordered Manganites

The low-energy excitations in the charge-ordered phase of polycrystalline La0.25Ca0.75MnO3 are explored by frequency-domain terahertz spectroscopy. In the frequency range from 4 cm^-1 to 700 cm^-1 (energies 0.4 meV to 90 meV) and at temperatures down to 5 K, we do not detect any feature that can be associated with the collective response of the spatially modulated charge continuum. In the antiferromagnetically ordered phase, broad absorption bands appear in the conductivity and permittivity spectra around 30 cm^-1 and 100 cm^-1 which are assigned to former acoustic phonons optically activated due to a fourfold superstructure in the crystal lattice. Our results indicate that characteristic energies of collective excitations of the charge-ordered phase in La0:25Ca0:75MnO3, if any, lie below 1 meV. At our lowest frequencies of only few wavenumbers a strong relaxation is observed above 100 K connected to the formation of the charge-ordered state.Comment: 5 pages, 3 figure

Origin of non-exponential relaxation in a crystalline ionic conductor: a multi-dimensional 109Ag NMR study

The origin of the non-exponential relaxation of silver ions in the crystalline ion conductor Ag7P3S11 is analyzed by comparing appropriate two-time and three-time 109Ag NMR correlation functions. The non-exponentiality is due to a rate distribution, i.e., dynamic heterogeneities, rather than to an intrinsic non-exponentiality. Thus, the data give no evidence for the relevance of correlated back-and-forth jumps on the timescale of the silver relaxation.Comment: 4 pages, 3 figure

Hopping Transport in the Presence of Site Energy Disorder: Temperature and Concentration Scaling of Conductivity Spectra

Recent measurements on ion conducting glasses have revealed that conductivity spectra for various temperatures and ionic concentrations can be superimposed onto a common master curve by an appropriate rescaling of the conductivity and frequency. In order to understand the origin of the observed scaling behavior, we investigate by Monte Carlo simulations the diffusion of particles in a lattice with site energy disorder for a wide range of both temperatures and concentrations. While the model can account for the changes in ionic activation energies upon changing the concentration, it in general yields conductivity spectra that exhibit no scaling behavior. However, for typical concentrations and sufficiently low temperatures, a fairly good data collapse is obtained analogous to that found in experiment.Comment: 6 pages, 4 figure

Complex lithium ion dynamics in simulated LiPO3 glass studied by means of multi-time correlation functions

Molecular dynamics simulations are performed to study the lithium jumps in LiPO3 glass. In particular, we calculate higher-order correlation functions that probe the positions of single lithium ions at several times. Three-time correlation functions show that the non-exponential relaxation of the lithium ions results from both correlated back-and-forth jumps and the existence of dynamical heterogeneities, i.e., the presence of a broad distribution of jump rates. A quantitative analysis yields that the contribution of the dynamical heterogeneities to the non-exponential depopulation of the lithium sites increases upon cooling. Further, correlated back-and-forth jumps between neighboring sites are observed for the fast ions of the distribution, but not for the slow ions and, hence, the back-jump probability depends on the dynamical state. Four-time correlation functions indicate that an exchange between fast and slow ions takes place on the timescale of the jumps themselves, i.e., the dynamical heterogeneities are short-lived. Hence, sites featuring fast and slow lithium dynamics, respectively, are intimately mixed. In addition, a backward correlation beyond the first neighbor shell for highly mobile ions and the presence of long-range dynamical heterogeneities suggest that fast ion migration occurs along preferential pathways in the glassy matrix. In the melt, we find no evidence for correlated back-and-forth motions and dynamical heterogeneities on the length scale of the next-neighbor distance.Comment: 12 pages, 13 figure

Colossal dielectric constants in transition-metal oxides

Many transition-metal oxides show very large ("colossal") magnitudes of the dielectric constant and thus have immense potential for applications in modern microelectronics and for the development of new capacitance-based energy-storage devices. In the present work, we thoroughly discuss the mechanisms that can lead to colossal values of the dielectric constant, especially emphasising effects generated by external and internal interfaces, including electronic phase separation. In addition, we provide a detailed overview and discussion of the dielectric properties of CaCu3Ti4O12 and related systems, which is today's most investigated material with colossal dielectric constant. Also a variety of further transition-metal oxides with large dielectric constants are treated in detail, among them the system La2-xSrxNiO4 where electronic phase separation may play a role in the generation of a colossal dielectric constant.Comment: 31 pages, 18 figures, submitted to Eur. Phys. J. for publication in the Special Topics volume "Cooperative Phenomena in Solids: Metal-Insulator Transitions and Ordering of Microscopic Degrees of Freedom