arXiv subjects

F. Cordero

Publications and source records attributed to F. Cordero.

At least 19 recordsLinked to original sources

arXiv2019

Probing ferroelectricity in highly conducting materials through their elastic response: persistence of ferroelectricity in metallic BaTiO3-d

The question whether ferroelectricity (FE) may coexist with a metallic or highly conducting state, or rather it must be suppressed by the screening from the free charges, is the focus of a rapidly increasing number of theoretical studies and is finally receiving positive experimental responses. The issue is closely related to the thermoelectric and multiferroic (also magnetic) applications of FE materials, where the electrical conductivity is required or spurious. In these circumstances, the traditional methods for probing ferroelectricity are hampered or made totally ineffective by the free charges, which screen the polar response to an external electric field. This fact may explain why more than 40 years passed between the first proposals of FE metals and the present experimental and theoretical activity. The measurement of the elastic moduli, Young's modulus in the present case, versus temperature is an effective method for studying the influence of doping on a FE transition because the elastic properties are unaffected by electrical conductivity. In this manner, it is shown that the FE transitions of BaTiO3-d are not suppressed by electron doping through O vacancies; only the onset temperatures are depressed, but the magnitudes of the softenings, and hence of the piezoelectric activity, are initially even increased.

cond-mat.mtrl-sci↗

arXiv2017

Quantitative evaluation of the piezoelectric response of unpoled ferroelectric ceramics from elastic and dielectric measurements: tetragonal BaTiO$_3$

A method for evaluating the piezoelectric response of unpoled ferroelectric ceramics from elastic and dielectric measurements is proposed and tested on BaTiO$_3$. The method is based on the observation that the softening in a ferroelectric phase with respect to the paraelectric phase is of piezoelectric origin. The angular averages of the piezoelectric softening in unpoled ceramics are calculated for ferroelectric phases of different symmetries. The expression of the orientational average with the piezoelectric and dielectric constants of single crystal tetragonal BaTiO$_3$ from the literature reproduces well the softening of the Young's modulus of unpoled ceramic BaTiO$_3$, after a correction for the porosity. The agreement is good in the temperature region sufficiently far from the Curie temperature and from the transition to the orthorhombic phase, where the effect of fluctuations should be negligible, but deviations are found outside this region, and the reason for this is discussed. This validates the determination of the piezoelectric response by means of purely elastic measurements on unpoled samples. The method is indirect and, for quantitative assessments, requires the knowledge of the dielectric tensor. On the other hand, it does not require poling of the sample, and therefore is insensitive to inaccuracies from incomplete poling, and can even be used with materials that cannot be poled, for example due to excessive electrical conductivity. While the proposed example of the Young's modulus of a ceramic provides an orientational average of all the single crystal piezoelectric constants, a Resonant Ultrasound Spectroscopy measurement of a single unpoled ceramic sample through the ferroelectric transition can in principle measure all the piezoelectric constants, together with the elastic ones.

cond-mat.mtrl-sci↗

arXiv2016

Rotational instability of the electric polarization and divergence of the shear elastic compliance

The rotational instability of the electric polarization P during phase transformations between ferroelectric phases is of great practical interest, since it may be accompanied by extremely large values of the piezoelectric coefficient, and a divergence of the coupled shear compliance contributes to such enhancements. In the literature, this had been explicitly calculated in the framework of the Landau theory and discussed with specific numerical simulations involving tetragonal, orthorhombic and rhombohedral ferroelectric phases. When monoclinic phases are involved, such an approach is practically impossible, and an approximated treatment had been proposed, based on the observation that in those cases there are shear strains almost linearly coupled to the transverse component of P, implying a divergence of the Curie-Weiss type in the associated compliances. Here the argument is extended to the general case of transitions whose major effect is a rotation of the polarization, and the limits of its validity are discussed. As experimental verification, the elastic response of BaTiO3 is measured and analyzed, together with those of other ferroelectric perovskites available in the literature, like KNN.

cond-mat.mtrl-sci↗

arXiv2016

Piezoelectric softening in ferroelectrics: ferroelectric versus antiferroelectric PbZr$_{1-x}$Ti$_{x}$O$_{3}$

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.

cond-mat.mtrl-sci↗

arXiv2014

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.

cond-mat.mtrl-sci↗

arXiv2012

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<111> 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.

cond-mat.mtrl-sci↗

arXiv2012

On the recently proposed martensitic-like structural transformation in V, Nb, and Ta

A recent announcement [Phys. Rev. Lett. 107, 075503, (2011)], after anomalies in the thermal expansion, of a previously unknown martensitic transformation in pure Nb, Ta and V is discussed in the light of anelastic measurements on Nb samples with comparable purities. It results that the effects of the alleged transformation on the anelastic spectra would be at least three orders of magnitude smaller than in typical martensitic transformations. A possible alternative explanation for the observed anomalies is proposed in terms of precipitation of unnoticed residual H.

cond-mat.mtrl-sci↗

arXiv2011

Anelastic spectroscopy study of the metal-insulator transition of Nd(1-x)EuxNiO3

Measurements are presented of the complex dynamic Young's modulus of NdNiO3 and Nd0.65Eu0.35NiO3 through the Metal-Insulator Transition (MIT). On cooling, the modulus presents a narrow dip at the MIT followed by an abrupt stiffening of ~6%. The anomaly is reproducible between cooling and heating in Nd0:65Eu0:35NiO3 but only appears as a slow stiffening during cooling in undoped NdNiO3, conformingly with the fact that the MIT in RNiO3 changes from strongly first order to second order when the mean R size is decreased. The elastic anomaly seems not to be associated with the antiferromagnetic transition, which is distinct from the MIT in Nd0.65Eu0.35NiO3. It is concluded that the steplike stiffening is due to the disappearance or freezing of dynamic Jahn- Teller (JT) distortions through the MIT, where the JT active Ni3+ is disproportionated into alternating Ni3+d and Ni3-d. The fluctuating octahedral JT distortion necessary to justify the observed jump in the elastic modulus is estimated as ~3%, but does not have a role in determining the MIT, since the otherwise expected precursor softening is not observed.

cond-mat.str-el↗

arXiv2011

Octahedral tilting, monoclinic phase and the phase diagram of PZT

Anelastic and dielectric spectroscopy measurements on PZT close to the morphotropic (MPB) and antiferroelectric boundaries provide new insight in some controversial aspects of its phase diagram. No evidence is found of a border separating monoclinic (M) from rhombohedral (R) phases, in agreement with recent structural studies supporting a coexistence of the two phases over a broad composition range x < 0.5, with the fraction of M increasing toward the MPB. It is also discussed why the observed maximum of elastic compliance appears to be due to a rotational instability of the polarisation and therefore cannot be explained by extrinsic softening from finely twinned R phase alone, but indicates the presence also of M phase, not necessarily homogeneous. A new diffuse transition is found within the ferroelectric phase near x ~ 0.1, at a temperature T_IT higher than the well established boundary T_T to the phase with tilted octahedra. It is proposed that around T_IT the octahedra start rotating in a disordered manner and finally become ordered below T_T. In this interpretation, the onset temperature for octahedral tilting monotonically increases up to the antiferroelectric transition of PbZrO3, and the depression of T_T(x) below x = 0.18 would be a consequence of the partial relieve of the mismatch between the cation radii with the initial stage of tilting below T_IT.

cond-mat.mtrl-sci↗

arXiv2010

Metal-insulator transition in Nd1-xEuxNiO3 probed by specific heat and anelastic measurements

Oxides RNiO3 (R = rare-earth, R # La) exhibit a metal-insulator (MI) transition at a temperature TMI and an antiferromagnetic (AF) transition at TN. Specific heat (CP) and anelastic spectroscopy measurements were performed in samples of Nd1-xEuxNiO3, 0 <= x <= 0.35. For x = 0, a peak in CP is observed upon cooling and warming at essentially the same temperature TMI = TN ~ 195 K, although the cooling peak is much smaller. For x >= 0.25, differences between cooling and warming curves are negligible, and two well defined peaks are clearly observed: one at lower temperatures, that define TN, and the other one at TMI. An external magnetic field of 9 T had no significant effect on these results. The elastic compliance (s) and the reciprocal of the mechanical quality factor (Q^-1) of NdNiO3, measured upon warming, showed a very sharp peak at essentially the same temperature obtained from CP, and no peak is observed upon cooling. The elastic modulus hardens below TMI much more sharply upon warming, while the cooling and warming curves are reproducible above TMI. On the other hand, for the sample with x = 0.35, s and Q^-1 curves are very similar upon warming and cooling. The results presented here give credence to the proposition that the MI phase transition changes from first to second order with increasing Eu doping.

cond-mat.str-el↗

arXiv2010

Effect of doping and oxygen vacancies on the octahedral tilt transitions in the BaCeO3 perovskite

We present a systematic study of the effect of Y doping and hydration level on the structural transformations of BaCeO3 based on anelastic spectroscopy experiments. The temperature of the intermediate transformation between rhombohedral and orthorhombic Imma phases rises with increasing the molar fraction x of Y roughly as (500 K)x in the hydrated state, and is depressed of more than twice that amount after complete dehydration. This is explained in terms of the effect of doping on the average (Ce/Y)-O and Ba-O bond lengths, and of lattice relaxation from O vacancies. The different behavior of the transition to the lower temperature Pnma orthorhombic phase is tentatively explained in terms of progressive flattening of the effective shape of the OH ion and ordering of the O vacancies during cooling.

cond-mat.mtrl-sci↗

arXiv2010

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.

cond-mat.mtrl-sci↗

arXiv2008

Hydrogen tunneling in the perovskite ionic conductor BaCe(1-x)Y(x)O(3-d)

We present low-temperature anelastic and dielectric spectroscopy measurements on the perovskite ionic conductor BaCe(1-x)Y(x)O(3-x/2) in the protonated, deuterated and outgassed states. Three main relaxation processes are ascribed to proton migration, reorientation about an Y dopant and tunneling around a same O atom. An additional relaxation maximum appears only in the dielectric spectrum around 60 K, and does not involve H motion, but may be of electronic origin, e.g. small polaron hopping. The peak at the lowest temperature, assigned to H tunneling, has been fitted with a relaxation rate presenting crossovers from one-phonon transitions, nearly independent of temperature, to two-phonon processes, varying as T^7, to Arrhenius-like. Substituting H with D lowers the overall rate by 8 times. The corresponding peak in the dielectric loss has an intensity nearly 40 times smaller than expected from the classical reorientation of the electric dipole associated with the OH complex. This fact is discussed in terms of coherent tunneling states of H in a cubic and orthorhombically distorted lattice, possibly indicating that only H in the symmetric regions of twin boundaries exhibit tunneling, and in terms of reduction of the effective dipole due to lattice polarization.

cond-mat.mtrl-sci↗

arXiv2007

Hopping and clustering of oxygen vacancies in SrTiO3 by anelastic relaxation

The complex elastic compliance s11(w,T) of SrTiO3-d has been measured as a function of the O deficiency d < 0.01. The two main relaxation peaks in the absorption are identified with hopping of isolated O vacancies over a barrier of 0.60 eV and reorientation of pairs of vacancies involving a barrier of 1 eV. The pair binding energy is ~0.2 eV and indications for additional clustering, possibly into chains, is found already at d ~0.004. The anistropic component of the elastic dipole of an O vacancy is Deltalambda = 0.026.

cond-mat.mtrl-sci↗

arXiv2007

Low-temperature phase transformations of PZT in the morphotropic phase-boundary region

We present anelastic and dielectric spectroscopy measurements of PbZr(1-x)Ti(x)O(3) with 0.455 < x < 0.53, which provide new information on the low temperature phase transitions. The tetragonal-to-monoclinic transformation is first-order for x < 0.48 and causes a softening of the polycrystal Young's modulus whose amplitude may exceed the one at the cubic-to-tetragonal transformation; this is explainable in terms of linear coupling between shear strain components and tilting angle of polarization in the monoclinic phase. The transition involving rotations of the octahedra below 200 K is visible both in the dielectric and anelastic losses, and it extends within the tetragonal phase, as predicted by recent first-principle calculations.

cond-mat.mtrl-sci↗

arXiv2006

Mechanical and Dielectric Response of PZT and Tetragonal to Monoclinic Phase Transition: I. Theory

The PZT material near the morphotropic phase boundary where a monoclinic phase was observed is studied. A theory of the tetragonal to monoclinic phase transition was developed within the Landau free energy approach. The phase transition from the tetragonal to the monoclinic phase is of the first order near the second order. Dielectric response near the phase transition from the tetragonal to the monoclinic phase was studied for the crystal and for the ceramic and polycrystalline material taking into account the diagonal 33 and the off diagonal 31 components of susceptibility. The later diverges at temperature of stability boundary for the monoclinic phase, and it is zero in the tetragonal phase. Such a behavior is not observed in the effective dielectric static constant for ceramics and polycrystalline materials. We explain absence of a large contribution of the off diagonal susceptibility by a grain structure of the material. Above the percolation transition the off diagonal contribution to the effective susceptibility is not present. Effective susceptibility which is decreasing in tetragonal phase is in the monoclinic phase also decreasing, however below phase transition temperature the decrease is slower. A quantitative theoretical behavior of dielectric susceptibility for both phases is found. Mechanical response of PZT material to a uniaxial stress is studied theoreticaly for both phases. Observed temperature behavior of it, a well around the transition temperature from the tetragonal to monoclinic phase transition, is qualitatively explained.

cond-mat.mtrl-sci↗

arXiv2006

High temperature memory in (Pb/La)(Zr/Ti)O_3 as intrinsic of the relaxor state rather than due to defect relaxation

It has been recently shown that the memory of multiple aging stages, a phenomenon considered possible only below the glass transition of some glassy systems, appears also above that temperature range in the relaxor ferroelectric (Pb/La)(Zr/Ti)O_3 (PLZT). Doubts exist whether memory at such high temperature is intrinsic of the glassy relaxor state or is rather due to migration of mobile defects. It is shown that the memory in the electric susceptibility and elastic compliance of PLZT 9/65/35 is not enhanced but depressed by mobile defects like O vacancies, H defects and mobile charges resulting from their ionization. In addition, memory is drastically reduced at La contents slightly below the relaxor region of the phase diagram, unless aging is protracted for long times (months at room temperature). This is considered as evidence that in the non relaxor case memory is indeed due to slow migration of defects, while in the La rich case it is intrinsic of the relaxor state, even above the temperature of the susceptibility maximum.

cond-mat.mtrl-sci↗

arXiv2006

Anelastic spectroscopy studies of high-Tc superconductors

YBCO, LSCO and Ru-1212 have been extensively studied by measuring the complex dynamic Young's modulus at 0.5-20 kHz between 1 and 900 K. The elastic energy loss is peaked at the temperatures where the relaxation rate of any microscopic process coupled to strain equals the measuring frequency. The reliability of the anelastic experiments and of the assignments to various microscopic mechanisms is also discussed. In LSCO, the layers of octahedra present solitonic tilt waves and fast local motion. The latter is driven by atomic tunneling and is enormously enhanced and accelerated by doping, demonstrating direct coupling between tilt modes and hole excitations. The dynamics of the hole stripes has been probed when they act as walls between domains of antiferromagnetically correlated spins (cluster spin glass) at LHe temperature, and at higher temperature, when they overcome by thermal activation the pinning barriers provided by Sr dopants. In YBCO various diffusion and ordering processes of the O atoms in the CuOx planes are identified, involving: i) Cu-O chains in the orthorhombic O-I phase (x~1); ii) sparser chains fragments at lower O content; iii) isolated O atoms. The hopping barriers are ~1 eV for the first two types of jumps and 0.11 eV for the latter. It is discussed how such widely different barriers are possible and how the extraordinarily high mobility of isolated O atoms is compatible with slow O ordering. In addition, relaxation processes have been attributed to hopping of O between off-center positions within the Cu-O chains and to bipolarons on orbitals that do not contribute to superconductivity. The O mobility in the RuO2-d planes of Ru-1212 is explained in terms of hopping of O vacancies whose elastic quadrupoles are weakly interacting and start becoming parallel to each other below TC ~ 470 K.

cond-mat.supr-con↗