Giant and isotropic magnetoresistance as huge as −53% was observed in magnetic manganese oxide La0.72Ca0.25MnOz films with an intrinsic antiferromagnetic spin structure. We ascribe this magnetoresistance to spin‐dependent electron scattering due to spin canting of the manganese oxide.

31p-S-4 Giant Magnetoresistance in Magnetic Manganese Oxide with Intrinsic Antiferromagnetic Spin Structure

▪ Abstract This account reviews the discovery, synthesis, properties, and the latest research advances of carbon nanotubes developed over the past 12 years. Because of their remarkable electronic and mechanical properties, carbon nanotubes are unique and exciting. The field has been developed rapidly, and the number of publications per year is increasing almost exponentially. Various technological applications are likely to arise using nanotubes for fabrication of flat panel displays, gas storage devices, toxic gas sensors, Li+ batteries, robust and lightweight composites, conducting paints, electronic nanodevices, etc. Further experimental and theoretical research is still necessary so that novel technologies will become a reality in the early twenty-first century.

Science and Technology of the Twenty-First Century: Synthesis, Properties, and Applications of Carbon Nanotubes

The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb+In) co-doped TiO₂ rutile, that exhibits a largely temperature- and frequency-independent colossal permittivity (> 10(4)) as well as a low dielectric loss (mostly < 0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that 'triangular' In₂(3+)Vo(••)Ti(3+) and 'diamond' shaped Nb₂(5+)Ti(3+)A(Ti) (A = Ti(3+)/In(3+)/Ti(4+)) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO₂. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.

Electron-pinned defect-dipoles for high-performance colossal permittivity materials

Fe-doped TiO 2 (Fe-TiO 2 ) nanorods were prepared by an impregnating-calcination method using the hydrothermally prepared titanate nanotubes as precursors and Fe(NO 3 ) 3 as dopant. The as-prepared samples were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, N 2 adsorption–desorption isotherms and UV–vis spectroscopy. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone in air under visible-light irradiation. The results show that Fe-doping greatly enhance the visible-light photocatalytic activity of mesoporous TiO 2 nanorods, and when the atomic ratio of Fe/Ti ( R Fe ) is in the range of 0.1–1.0%, the photocatalytic activity of the samples is higher than that of Degussa P25 and pure TiO 2 nanorods. At R Fe  = 0.5%, the photocatalytic activity of Fe-TiO 2 nanorods exceeds that of Degussa P25 by a factor of more than two times. This is ascribed to the fact that the one-dimensional nanostructure can enhance the transfer and transport of charge carrier, the Fe-doping induces the shift of the absorption edge into the visible-light range with the narrowing of the band gap and reduces the recombination of photo-generated electrons and holes. Furthermore, the first-principle density functional theory (DFT) calculation further confirms the red shift of absorption edges and the narrowing of band gap of Fe-TiO 2 nanorods.

Preparation, characterization and visible-light-driven photocatalytic activity of Fe-doped titania nanorods and first-principles study for electronic structures

Carbon nanotubes are promising materials for various applications. In recent years, progress in manufacturing and functionalizing carbon nanotubes has been made to achieve the control of bulk and surface properties including the wettability, acid–base properties, adsorption, electric conductivity and capacitance. In order to gain the optimal benefit of carbon nanotubes, comprehensive understanding on manufacturing and functionalizing carbon nanotubes ought to be systematically developed. This review summarizes methodologies of manufacturing carbon nanotubes via arc discharge, laser ablation and chemical vapor deposition and functionalizing carbon nanotubes through surface oxidation and activation, doping of heteroatoms, halogenation, sulfonation, grafting, polymer coating, noncovalent functionalization and nanoparticle attachment. The characterization techniques detecting the bulk nature and surface properties as well as the effects of various functionalization approaches on modifying the surface properties for specific applications in catalysis including heterogeneous catalysis, photocatalysis, photoelectrocatalysis and electrocatalysis are highlighted.

Carbon nanotube catalysts: recent advances in synthesis, characterization and applications.

The dielectric properties of $\mathrm{Ca}{\mathrm{Cu}}_{3}{\mathrm{Ti}}_{4}{\mathrm{O}}_{12}$, a material showing colossal values of the dielectric constant, were investigated over a broad temperature and frequency range extending up to $1.3\phantom{\rule{0.3em}{0ex}}\mathrm{GHz}$. A detailed equivalent-circuit analysis of the results and two crucial experiments, employing different types of contacts and varying the sample thickness were performed. The results provide clear evidence that the apparently high values of the dielectric constant in $\mathrm{Ca}{\mathrm{Cu}}_{3}{\mathrm{Ti}}_{4}{\mathrm{O}}_{12}$ are nonintrinsic and due to electrode polarization effects. The intrinsic properties of $\mathrm{Ca}{\mathrm{Cu}}_{3}{\mathrm{Ti}}_{4}{\mathrm{O}}_{12}$ are characterized by charge transport via hopping of localized charge carriers and a relatively high dielectric constant of the order of 100.

Nonintrinsic origin of the colossal dielectric constants in Ca Cu 3 Ti 4 O 12

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...

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, including so far only rarely investigated single crystalline material. 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 are investigated. Broadband spectra of a single crystal are analyzed by an equivalent circuit description, 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, also is strongly affected by the applied ac voltage. Concerning the origin of the two insulating layers, we discuss a completely surface-related mechanism assuming the formation of a metal-insulator diode and a combination of surface and internal barriers.

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.

/pdf/broadband-dielectric-spectroscopy-on-single-crystalline-and-2qwzajezmx.pdf

Stefan G. Ebbinghaus

Papers

Nonintrinsic origin of the colossal dielectric constants in Ca Cu 3 Ti 4 O 12

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

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

Broadband dielectric spectroscopy on single-crystalline and ceramic CaCu3Ti4O12

The vast colour spectrum of ternary metal oxynitride pigments