No Arabic abstract
In this work, we address the issue of peaking of piezoelectric response at a particular composition in the morphotropic phase boundary (MPB) region of (Pb0.940Sr0.06)(ZrxTi1-x)O3 (PSZT) piezoelectric ceramics. We present results of synchrotron x-ray powder diffraction, dielectric, piezoelectric and sound velocity studies to critically examine the applicability of various models for the peaking of physical properties. It is shown that the models based on the concepts of phase coexistence, polarization rotation due to monoclinic structure, tricritical point and temperature dependent softening of elastic modulus may enhance the piezoelectric response in the MPB region in general but cannot explain its peaking at a specific composition. Our results reveal that the high value of piezoelectric response for the MPB compositions in PSZT at x=0.530 is due to the softening of the elastic modulus as a function of composition. The softening of elastic modulus facilitates the generation of large piezoelectric strain and polarization on approaching the MPB composition of x=0.530. This new finding based on the softening of elastic modulus may pave the way forward for discovering/designing new lead-free environmentally friendly piezoelectric materials and revolutionize the field of piezoelectric ceramics.
The antiferrodistortive (AFD) phase transition for a pseudotetragonal composition of Pb(Zr0.530Ti0.470)O3 (PZT) doped with 6% Sr has been investigated using sound velocity (4 to 320K), high resolution synchrotron X-ray powder diffraction (100 to 800K) and high resolution as well as high flux neutron powder diffraction measurements (4K) to settle the existing controversies about the true ground state of PZT in the morphotropic phase boundary (MPB) region. The multiplet character of the neutron diffraction profiles of (3/2 1/2 1/2)pc (pseudocubic or pc indices) and (3/2 3/2 1/2)pc superlattice peaks, appearing below the AFD transition temperature, rules out the rhombohedral R3c space group. The true ground state is confirmed to be monoclinic in the Cc space group in agreement with the predictions of the first principles calculations and earlier findings for pure PZT in the MPB region. 6% Sr2+ substitution and the use of high wavelength ({lambda}=2.44{AA}) neutrons have played key role in settling the existing controversies about the true ground state of PZT in the MPB region.
Temperature dependent structural changes in a nearly pure monoclinic phase composition (x=0.525) of Pb(Zr_xTi_1-x)O_3 (PZT) have been investigated using Rietveld analysis of high-resolution synchrotron powder x-ray diffraction data and correlated with changes in the dielectric constant and planar electromechanical coupling coefficient. Our results show that the intrinsic piezoelectric response of the tetragonal phase of PZT is higher than that of the monoclinic phase. It is also shown that the high piezoelectric response of PZT may be linked with an anomalous softening of the elastic modulus (1/S_11) of the tetragonal compositions closest to the morphotropic phase boundary.
We report here the structure and dielectric studies on a new lead free (1-x)BaTiO3-xBi(Mg1/2Zr1/2)O3 solid solution to explore the morphotropic phase boundary. The powder x-ray diffraction studies on (1-x)BaTiO3-xBi(Mg1/2Zr1/2)O3 solid solution suggests that structure is tetragonal (P4mm) for the composition with x=0.05 and cubic for the composition with x=0.30 and 0.40. Morphotropic phase boundary is observed in the composition range 0.10<x<0.30, where phase coexistence is observed and composition dependence of room temperature permittivity shows a peak. High temperature dielectric measurement for the composition with x=0.20 exhibits diffuse phase transition having peak temperature around ~ 396 K at 10 kHz. The diffuseness parameter ({gamma}) was obtained to be 1.68 for composition with x=0.20.
The symmetry was examined using neutron diffraction method on Pb(Zn1/3Nb2/3)O3 -9%PbTiO3 (PZN/9PT) which has a composition at the morphotropic phase boundary (MPB) between Pb(Zn1/3Nb2/3)O3 and PbTiO3. The results were compared with those of other specimens with same composition but with different prehistory. The equilibrium state of all examined specimens is not the mixture of rhombohedral and tetragonal phases of the end members but exists in a new polarization rotation line Mc# (orthorhombic-monoclinic line). Among examined specimens, one exhibited tetragonal symmetry at room temperature but recovered monoclinic phase after a cooling and heating cycle.
We demonstrate the robustness of polarization in ultrathin compressive strained BiFeO$_3$ single layers and heterostructures during epitaxial thin-film growth. Using in-situ optical second harmonic generation (ISHG), we explore the emergence of ferroelectric phases at the strain-driven morphotropic phase boundary in the ultrathin regime. We find that the epitaxial films grow in the ferroelectric tetragonal (T-) phase without exhibition of a critical thickness. The robustness of this high-temperature T-phase against depolarizing-field effects is further demonstrated during the growth of capacitor-like (metal|ferroelectric|metal) heterostructures. Using temperature-dependent ISHG post-deposition, we identify the thickness-dependent onset of the monoclinic distortion in the T-matrix and trace the signature of the subsequent emergence of the strain-relaxed rhombohedral-like monoclinic phase. Our results show that strain-driven T-phase stabilization in BiFeO$_3$ yields a prominent candidate material for realizing ultrathin ferroelectric devices.