S. Krohns

Colossal dielectric constants in transition-metal oxides

Abstract. 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.

Colossal dielectric constants in single-crystalline and ceramic CaCu3Ti4O12 investigated by broadband dielectric spectroscopy

In the present work, the authors report results of broadband dielectric spectroscopy on various samples of CaCu3Ti4O12 (CCTO), also including single-crystalline material, which so far was only rarely investigated. The measurements extend up to 1.3 GHz, covering more than nine frequency decades. We address the question of the origin of the colossal dielectric constants and of the relaxational behavior in this material, including the second relaxation reported in several recent works. For this purpose, the dependence of the temperature- and frequency-dependent dielectric properties on different tempering and surface treatments of the samples and on ac-field amplitude is investigated. Broadband spectra of a single crystal are analyzed by an equivalent circuit description by assuming two highly resistive layers in series to the bulk. Good fits could be achieved, including the second relaxation, which also shows up in single crystals. The temperature- and frequency-dependent intrinsic conductivity of CCTO is consistent with the variable range hopping model. The second relaxation is sensitive to surface treatment and, in contrast to the main relaxation, is also strongly affected by the applied ac voltage. Concerning the origin of the two insulating layers, we discuss a completely surface-related mechanism by assuming the formation of a metal-insulator diode and a combination of surface and internal barriers.In the present work, the authors report results of broadband dielectric spectroscopy on various samples of CaCu3Ti4O12 (CCTO), also including single-crystalline material, which so far was only rarely investigated. The measurements extend up to 1.3 GHz, covering more than nine frequency decades. We address the question of the origin of the colossal dielectric constants and of the relaxational behavior in this material, including the second relaxation reported in several recent works. For this purpose, the dependence of the temperature- and frequency-dependent dielectric properties on different tempering and surface treatments of the samples and on ac-field amplitude is investigated. Broadband spectra of a single crystal are analyzed by an equivalent circuit description by assuming two highly resistive layers in series to the bulk. Good fits could be achieved, including the second relaxation, which also shows up in single crystals. The temperature- and frequency-dependent intrinsic conductivity of CCTO is c...

Broadband dielectric spectroscopy on single-crystalline and ceramic CaCu3Ti4O12

The authors present dielectric measurements of the colossal dielectric constant material CaCu3Ti4O12 extending up to 1.3GHz also covering so far only rarely investigated single-crystalline samples. Special emphasis is put on the second relaxation reported in several works on polycrystals, which the authors detect also in single crystals. For polycrystalline samples, the authors provide a recipe to achieve values of the dielectric constant as high as in single crystals.

The route to resource-efficient novel materials

Combining the efforts of physicists, materials scientists, economists and resource-strategy researchers opens up an interdisciplinary route enabling the substitution of rare elements by more abundant ones, serving as a guideline for the development of novel materials.

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism

Multiferroics, showing simultaneous ordering of electrical and magnetic degrees of freedom, are remarkable materials as seen from both the academic and technological points of view. A prominent mechanism of multiferroicity is the spin-driven ferroelectricity, often found in frustrated antiferromagnets with helical spin order. There, as for conventional ferroelectrics, the electrical dipoles arise from an off-centre displacement of ions. However, recently a different mechanism, namely purely electronic ferroelectricity, where charge order breaks inversion symmetry, has attracted considerable interest. Here we provide evidence for ferroelectricity, accompanied by antiferromagnetic spin order, in a two-dimensional organic charge-transfer salt, thus representing a new class of multiferroics. We propose a charge-order-driven mechanism leading to electronic ferroelectricity in this material. Quite unexpectedly for electronic ferroelectrics, dipolar and spin order arise nearly simultaneously. This can be ascribed to the loss of spin frustration induced by the ferroelectric ordering. Hence, here the spin order is driven by the ferroelectricity, in marked contrast to the spin-driven ferroelectricity in helical magnets.

Electrode polarization effects in broadband dielectric spectroscopy

AbstractIn the present work, we provide broadband dielectric spectra showing strong electrode polarization effects for various materials, belonging to very different material classes. This includes both ionic and electronic conductors as, e.g., salt solutions, ionic liquids, human blood, and colossal-dielectric-constant materials. These data are intended to provide a broad data base enabling a critical test of the validity of phenomenological and microscopic models for electrode polarization. In the present work, the results are analyzed using a simple phenomenological equivalent-circuit description, involving a distributed parallel RC circuit element for the modeling of the weakly conducting regions close to the electrodes. Excellent fits of the experimental data are achieved in this way, demonstrating the universal applicability of this approach. In the investigated ionically conducting materials, we find the universal appearance of a second dispersion region due to electrode polarization, which is only revealed if measuring down to sufficiently low frequencies. This indicates the presence of a second charge-transport process in ionic conductors with blocking electrodes.

Broadband dielectric response of Ca Cu 3 Ti 4 O 12 : From dc to the electronic transition regime

We report on phonon properties and electronic transitions in CaCu3Ti4O12, a material which reveals a colossal dielectric constant at room temperature without any ferroelectric transition. The results of far- and mid-infrared measurements are compared to those obtained by broadband dielectric and millimeter-wave spectroscopy on the same single crystal. The unusual temperature dependence of phonon eigenfrequencies, dampings and ionic plasma frequencies of low lying phonon modes are analyzed and discussed in detail. Electronic excitations below 4 eV are identified as transitions between full and empty hybridized oxygen-copper bands and between oxygen-copper and unoccupied Ti 3d bands. The unusually small band gap determined from the dc-conductivity (~200 meV) compares well with the optical results.

Colossal dielectric constants: A common phenomenon in CaCu3Ti4O12 related materials

Abstract In the present work we demonstrate that in addition to the well-known colossal-dielectric-constant material CaCu3Ti4O12 various members of the series Ln2/3Cu3Ti4O12 with Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm also exhibit giant values of the dielectric constant. Just as CaCu3Ti4O12, all these materials show a Maxwell–Wagner type relaxation process. For the best material, Pr2/3Cu3Ti4O12, we provide a detailed investigation of its dielectric properties in a broad frequency range up to 1 GHz. Polarization at internal barriers, most likely grain boundaries, seems to be the reason for the observed very high values of the dielectric constant. Taking into account the present results and those reported in the literature, we conclude that CaCu3Ti4O12 is not exceptional at all and there seem to be various isostructural materials with similar dielectric properties.

Switching the ferroelectric polarization in theS=1∕2chain cuprateLiCuVO4by external magnetic fields

We present a detailed study of complex dielectric constant and ferroelectric polarization in multiferroic LiCuVO4 as function of temperature and external magnetic field. In zero external magnetic field, spiral spin order with an ab helix and a propagation vector along the crystallographic b direction is established, which induces ferroelectric order with spontaneous polarization parallel to a. The direction of the helix can be reoriented by an external magnetic field and allows switching of the spontaneous polarization. We find a strong dependence of the absolute value of the polarization for different orientations of the spiral plane. Above 7.5 T, LiCuVO4 reveals collinear spin order and remains paraelectric for all field directions. Thus this system is ideally suited to check the symmetry relations for spiral magnets as predicted theoretically. The strong coupling of ferroelectric and magnetic order is documented and the complex (B,T) phase diagram is fully explored.

Bananas go paraelectric

Using a banana as an example, we demonstrate how the ferroelectric-like hysteresis loops measured in inhomogeneous, conducting materials can easily be identified as non-intrinsic. With simple experiments, the response of a banana to electric fields is revealed as characteristic for an inhomogeneous paraelectric ion conductor. Not even absolute beginners in dielectrics should identify this biological matter as ferroelectric.