Lattice dielectric response of CdCu{3}Ti{4}O{12} and of CaCu{3}Ti{4}O{12} from first principles

Structural, vibrational, and lattice dielectric properties of CdCu{3}Ti{4}O{12} are studied using density-functional theory within the local spin-density approximation, and the results are compared with those computed previously for CaCu{3}Ti{4}O{12}. Replacing Ca with Cd is found to leave many calculated quantities largely unaltered, although significant differences do emerge in zone-center optical phonon frequencies and mode effective charges. The computed phonon frequencies of CdCu{3}Ti{4}O{12} are found to be in excellent agreement with experiment, and the computed lattice contribution to the intrinsic static dielectric constant (~60) also agrees exceptionally well with a recent optical absorption experiment. These results provide further support for a picture in which the lattice dielectric response is essentially conventional, suggesting an extrinsic origin for the anomalous low-frequency dielectric response recently observed in both materials.Comment: 5 pages; uses REVTEX macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/lh_cdct/index.htm

A novel heavy-fermion state in CaCu_3Ru_4O12

We have measured susceptibility, specific heat, resistivity, and thermopower of CaCu$_3$Ti$_{4-x}$Ru$_x$O$_{12}$ and CaCu$_{3-y}$Mn$_y$Ru$_4$O$_{12}$, and have found that CaCu$_3$Ru$_4$O$_{12}$ can be regarded as a heavy-fermion oxide in d-electron systems. The Kondo temperature is near 200 K, and the susceptibility (1.4$\times10^{-3}$ emu/Cu mol) and the electron specific heat coefficient (28 mJ/Cu molK$^2$) are moderately enhanced. The resistivity is proportional to $T^2$ at low temperatures, and satisfies the Kadowaki-Woods relation. The heavy-fermion state comes from the interaction between the localized moment of Cu 3d and the conduction electron of Ru 4d. An insulator-metal transition occurs between $x=1.5$ and 4 in CaCu$_3$Ti$_{4-x}$Ru$_x$O$_{12}$, which can be regarded as a transition from magnetic insulator to heavy-fermion metal.Comment: 4 pages, 5 figures, submitted to J. Phys. Soc. Jp

Heavy-Mass Behavior of Ordered Perovskites ACu3Ru4O12 (A = Na, Ca, La)

We synthesized ACu3Ru4O12 (A = Na, Na0.5Ca0.5, Ca, Ca0.5La0.5, La) and measured their DC magnetization, AC susceptibility, specific heat, and resistivity, in order to investigate the effects of the hetero-valent substitution. A broad peak in the DC magnetization around 200 K was observed only in CaCu3Ru4O12, suggesting the Kondo effect due to localized Cu2+ ions. However, the electronic specific heat coefficients exhibit large values not only for CaCu3Ru4O12 but also for all the other samples. Moreover, the Wilson ratio and the Kadowaki-Woods ratio of our samples are all similar to the values of other heavy-fermion compounds. These results question the Kondo effect as the dominant origin of the mass enhancement, and rather indicate the importance of correlations among itinerant Ru electrons.Comment: 6 pages, 6 figures, to be published in J. Phys. Soc. Jp

On the magnetism of Ln{2/3}Cu{3}Ti{4}O{12} (Ln = lanthanide)

The magnetic and thermodynamic properties of the complete Ln$_{2/3}$Cu$_3$Ti$_4$O$_{12}$ series were investigated. Here $Ln$ stands for the lanthanides La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. %Most of the compounds were prepared as single phase polycrystalline powder %without any traces of impurities. Marginal amounts of %impurities $(< 2$ were detected $Ln=$ Gd, Er, and Tm. %Significant amounts of impurity phases were found for $Ln=$ Ce and Yb. All the samples investigated crystallize in the space group $Im\bar{3}$ with lattice constants that follow the lanthanide contraction. The lattice constant of the Ce compound reveals the presence of Ce$^{4+}$ leading to the composition Ce$_{1/2}$Cu$_3$Ti$_4$O$_{12}$. From magnetic susceptibility and electron-spin resonance experiments it can be concluded that the copper ions always carry a spin $S=1/2$ and order antiferromagnetically close to 25\,K. The Curie-Weiss temperatures can approximately be calculated assuming a two-sublattice model corresponding to the copper and lanthanide ions, respectively. It seems that the magnetic moments of the heavy rare earths are weakly coupled to the copper spins, while for the light lanthanides no such coupling was found. The $4f$ moments remain paramagnetic down to the lowest temperatures, with the exception of the Tm compound, which indicates enhanced Van-Vleck magnetism due to a non-magnetic singlet ground state of the crystal-field split $4f$ manifold. From specific-heat measurements we accurately determined the antiferromagnetic ordering temperature and obtained information on the crystal-field states of the rare-earth ions. The heat-capacity results also revealed the presence of a small fraction of Ce$^{3+}$ in a magnetic $4f^1$ state.Comment: 10 pages, 10 figure

Correlations of structural, magnetic, and dielectric properties of undoped and doped CaCu3Ti4O12

The present work reports synthesis, as well as a detailed and careful characterization of structural, magnetic, and dielectric properties of differently tempered undoped and doped CaCu3Ti4O12 (CCTO) ceramics. For this purpose, neutron and x-ray powder diffraction, SQUID measurements, and dielectric spectroscopy have been performed. Mn-, Fe-, and Ni-doped CCTO ceramics were investigated in great detail to document the influence of low-level doping with 3d metals on the antiferromagnetic structure and dielectric properties. In the light of possible magnetoelectric coupling in these doped ceramics, the dielectric measurements were also carried out in external magnetic fields up to 7 T, showing a minor but significant dependence of the dielectric constant on the applied magnetic field. Undoped CCTO is well-known for its colossal dielectric constant in a broad frequency and temperature range. With the present extended characterization of doped as well as undoped CCTO, we want to address the question why doping with only 1% Mn or 0.5% Fe decreases the room-temperature dielectric constant of CCTO by a factor of ~100 with a concomitant reduction of the conductivity, whereas 0.5% Ni doping changes the dielectric properties only slightly. In addition, diffraction experiments and magnetic investigations were undertaken to check for possible correlations of the magnitude of the colossal dielectric constants with structural details or with magnetic properties like the magnetic ordering, the Curie-Weiss temperatures, or the paramagnetic moment. It is revealed, that while the magnetic ordering temperature and the effective moment of all investigated CCTO ceramics are rather similar, there is a dramatic influence of doping and tempering time on the Curie-Weiss constant.Comment: 10 pages, 11 figure

Deposition conditions for the growth of textured ZnO thin films by aerosol CVD process

The crystalline orientation of ZnO thin films deposited by an aerosol CVD process is studied with regard to the experimental conditions. The quality of the C-axis oriented growth depended on the substrate temperature, on the deposition rate and also on the hygrometric degree of the carrier gas. The quality of the gold sublayer influenced also the quality of the ZnO textured growth. Under a dry gas mixture N2-O2 at 495°C and with a deposition rate of 35Å/mn, the texture ratio was less than -3.5 and the misorientation σ002 was less than 1.6°