Effects of coupling between octahedral tilting and polar modes on the phase diagram of PbZr1-xTixO3 (PZT)

The results are presented of anelastic and dielectric spectroscopy measurements on large grain ceramic PZT with compositions near the two morphotropic phase boundaries (MPBs) that the ferroelectric (FE) rhombohedral phase has with the Zr-rich antiferroelectric and Ti-rich FE tetragonal phases. These results are discussed together with similar data from previous series of samples, and reveal new features of the phase diagram of PZT, mainly connected with octahedral tilting and its coupling with the polar modes. Additional evidence is provided of what we interpret as the onset of the tilt instability, when is initially frustrated by lattice disorder, and the long range order is achieved at lower temperature. Its temperature T_IT(x) prosecutes the long range tilt instability line T_T(x) up to T_C, when T_T. It is proposed that the difficulty of seeing the expected 1/2 modulations in diffraction experiments is due to the large correlation volume associated with that type of tilt fluctuations combined with strong lattice disorder. It is shown that the lines of the tilt instabilities tend to be attracted and merge with those of polar instabilities. Not only T_IT bends toward T_C and then merges with it, but in our series of samples the temperature T_MPB of the dielectric and anelastic maxima at the rhombohedral/tetragonal MPB does not cross T_T, but deviates remaining parallel or possibly merging with T_T. These features, together with a similar one in NBT-BT, are discussed in terms of cooperative coupling between tilt and FE instabilities, which may trigger a common phase transition. An analogy is found with recent simulations of the tilt and FE transitions in multiferroic BiFeO3. An abrupt change is found in the shape of the anelastic anomaly at T_T when x passes from 0.465 to 0.48, possibly indicative of a rhombohedral/monoclinic boundary.Comment: 15 pages, 11 figure

Piezoelectric softening in ferroelectrics: ferroelectric versus antiferroelectric PbZr1−x_{1-x}Tix_{x}O3_{3}

The traditional derivation of the elastic anomalies associated with ferroelectric (FE) phase transitions in the framework of the Landau theory is combined with the piezoelectric constitutive relations instead of being explicitly carried out with a definite expression of the FE part of the free energy. In this manner it is shown that the softening within the FE phase is of electrostrictive and hence piezoelectric origin. Such a piezoelectric softening may be canceled by the better known piezoelectric stiffening, when the piezoelectric charges formed during the vibration are accompanied by the depolarization field, as for example in Brillouin scattering experiments. As experimental validation, we present new measurements on Zr-rich PZT, where the FE phase transforms into antiferroelectric on cooling or doping with La, and a comparison of existing measurements made on FE PZT with low frequency and Brillouin scattering experiments

Effects of aging and annealing on the polar and antiferrodistortive components of the antiferroelectric transition in PZT

The antipolar and antiferrodistortive (AFD) components of the antiferroelectric (AFE) transition in PbZr1-xTixO3 (x=0.054) can occur separately and with different kinetics, depending on the sample history, and are accompanied by elastic softening and stiffening, respectively. Together with the softening that accompanies octahedral tilting in the fraction of phase that is not yet transformed into AFE, they give rise to a variety of shapes of the curves of the elastic compliance versus temperature. All such anomalies found in samples with x=0.046 and 0.054, in addition to those already studied at x=0.050, can be fitted consistently with a phenomenological model based on the simple hypothesis that each of the polar and AFD transitions produces a step in the elastic modulus, whose position in temperature and width reflect the progress of each transition. The slowing of the kinetics of the transformations is correlated with the formation of defect structures during aging in the ferroelectric or AFE state, which are also responsible for a progressive softening of the lattice with time and thermal cycling, until annealing at high temperature recovers the initial conditions

Optical Properties of Ar Ions Irradiated Nanocrystalline ZrC and ZrN Thin Films

Thin nanocrystalline ZrC and ZrN films (less than 400 nanometers), grown on (100) Si substrates at a substrate temperature of 500 degrees Centigrade by the pulsed laser deposition (PLD) technique, were irradiated by 800 kiloelectronvolts Ar ion irradiation with fluences from 1 times 10(sup 14) atoms per square centimeter up to 2 times 10(sup 15) atoms per square centimeter. Optical reflectance data, acquired from as-deposited and irradiated films, in the range of 500-50000 per centimeter (0.066 electronvolts), was used to assess the effect of irradiation on the optical and electronic properties. Both in ZrC and ZrN films we observed that irradiation affects the optical properties of the films mostly at low frequencies, which is dominated by the free carriers response. In both materials, we found a significant reduction in the free carriers scattering rate, i.e. possible increase in mobility, at higher irradiation flux. This is consistent with our previous findings that irradiation affects the crystallite size and the micro-strain, but it does not induce major structural changes

Bulk Fermi surface and electronic properties of Cu0.07_{0.07}Bi2_{2}Se3_{3}

The electronic properties of Cu$_{0.07}$Bi$_{2}$Se$_{3}$ have been investigated using Shubnikov-de Haas and optical reflectance measurements. Quantum oscillations reveal a bulk, three-dimensional Fermi surface with anisotropy $k^{c}_{F}/k^{ab}_{F}\approx$ 2 and a modest increase in free-carrier concentration and in scattering rate with respect to the undoped Bi$_{2}$Se$_{3}$, also confirmed by reflectivity data. The effective mass is almost identical to that of Bi$_{2}$Se$_{3}$. Optical conductivity reveals a strong enhancement of the bound impurity bands with Cu addition, suggesting that a significant number of Cu atoms enter the interstitial sites between Bi and Se layers or may even substitute for Bi. This conclusion is also supported by X-ray diffraction measurements, where a significant increase of microstrain was found in Cu$_{0.07}$Bi$_{2}$Se$_{3}$, compared to Bi$_{2}$Se$_{3}$.Comment: Accepted to Phys. Rev B (R

Phase transitions and phase diagram of the ferroelectric perovskite NBT-BT by anelastic and dielectric measurements

The complex elastic compliance and dielectric susceptibility of (Na_{0.5}Bi_{0.5})_{1-x}Ba_{x}TiO_{3} (NBT-BT) have been measured in the composition range between pure NBT and the morphotropic phase boundary included, 0 <= x <= 0.08. The compliance of NBT presents sharp peaks at the rhombohedral/tetragonal and tetragonal/cubic transitions, allowing the determination of the tetragonal region of the phase diagram, up to now impossible due to the strong lattice disorder and small distortions and polarizations involved. In spite of ample evidence of disorder and structural heterogeneity, the R-T transition remains sharp up to x = 0.06, whereas the T-C transition merges into the diffuse and relaxor-like transition associated with broad maxima of the dielectric and elastic susceptibilities. An attempt is made at relating the different features in the anelastic and dielectric curves to different modes of octahedral rotations and polar cation shifts. The possibility is also considered that the cation displacements locally have monoclinic symmetry, as for PZT near the morphotropic phase boundary.Comment: 11 pages, 9 figures, submitted to Phys. Rev.