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Register a new userMultiple soft-mode vibrations of lead zirconate
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Polarized Raman, IR and time-domain THz spectroscopy of orthorhombic lead zirconate single crystals yielded a comprehensive picture of temperature-dependent quasiharmonic frequencies of its low-frequency phonon modes. It is argued that these modes primarily involve vibration of Pb and/or oxygen octahedra librations and their relation to particular phonon modes of the parent cubic phase is proposed. Counts of the observed IR and Raman active modes belonging to distinct irreducible representations agree quite well with group-theory predictions. The most remarkable finding is the considerably enhanced frequency renormalization of the y-polarized polar modes, resulting in a pronounced low temperature dielectric anisotropy. Results are discussed in terms of contemporary phenomenological theory of antiferroelectricity.
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Hyper-Raman scattering experiments allowed collecting the spectra of the lowest F1u-symmetry mode of PbTiO3 crystal in the paraelectric phase up to 930K as well as down to about 1K above the phase transition. It is realized that this mode is fully responsible for the Curie-Weiss behavior of its dielectric permittivity above Tc. Near the phase transition, this phonon frequency softens down to 17 cm-1 and its spectrum can be well modeled as a response of a single damped harmonic oscillator. It is concluded that PbTiO3 constitutes a clean example of a soft mode-driven ferroelectric system.
Neutron diffraction data obtained on single crystals of PbZr1-xTixO3 with x = 0.325 and x = 0.460, which lie on the pseudorhombohedral side of the morphotropic phase boundary, suggest a coexistence of rhombohedral (R3m/R3c) and monoclinic (Cm) domains and that monoclinic order is enhanced by Ti substitution. A monoclinic phase with a doubled unit cell (Cc) is ruled out as the ground state.
Renewed interest has been witnessed in utilizing the piezoelectric response of $PbZr_{0.52}Ti_{0.48}O_{3}$ (PZT) films on glass substrates for applications such as data storage and adaptive optics. Accordingly, new methodologies are being explored to grow well-oriented PZT thin films to harvest a large piezoelectric response. However, thin film piezoelectric response is significantly reduced compared to intrinsic response due to substrate induced clamping, even when films are well-oriented. Here, a novel method is presented to grow preferentially (100)-oriented PZT films on glass substrates by utilizing crystalline nanosheets as seed layers. Furthermore, increasing the repetition frequency up to 20 Hz during pulsed laser deposition helps to tune the film microstructure to hierarchically ordered columns that leads to reduced clamping and enhanced piezoelectric response evidenced by transmission electron microscopy and analytical calculations. A large piezoelectric response of 280 pm/V is observed in optimally tuned structure which almost triples the highest reported piezoelectric response on glass. To confirm that the clamping compromises the piezoelectric response, denser films are deposited using a lower repetition frequency and a $BiFeO_{3}$ buffer layer resulting in significantly reduced piezoelectric responses. This paper demonstrates a novel method for PZT integration on glass substrates without compromising the large piezoelectric response.
The effect of polarization fatigue on the Rayleigh coefficients of ferroelectric lead zirconate titanate (PZT) thin film was systematically investigated. It was found that electrical fatigue strongly affects the Rayleigh behaviour of the PZT film. Both the reversible and irreversible Rayleigh coefficients decrease with increasing the number of switching cycles. This phenomenon is attributed to the growth of an interfacial degraded layer between the electrode and the film during electrical cycling. The methodology used in this work could serve as an alternative non-destructive way for evaluating the fatigue endurance and degradation in dielectric properties of ferroelectric thin-film devices during applications.
By means of non-resonant Raman spectroscopy and density functional theory calculations, we measure and assign the vibrational spectrum of two distinct two-dimensional lead-iodide perovskite derivatives. These two samples are selected in order to probe the effects of the organic cation on lattice dynamics. One templating cation is composed of a phenyl-substituted ammonium derivative, while the other contains a linear alkyl group. We find that modes that directly involve the organic cation are more prevalent in the phenyl-substituted derivative. Comparison of the temperature dependence of the Raman spectra reveals differences in the nature of dynamic disorder, with a strong dependence on the molecular nature of the organic moiety.
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