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The morphotropic phase boundary composition Bi1/2Na1/2TiO3-20 mol. % Bi1/2Na1/2TiO3 was chosen as initial material to do selective A-site aliovalent doping replacing Na and K by 1 at. % La, respectively. The materials were studied macroscopically by measuring dielectric and electromechanical properties. The Na-replaced material has a lower freezing temperature Tfr, lower remanent polarization and remanent strain, and thus a higher degree of ergodicity than the K-replaced material. These results are contrasted with local poling experiments and hysteresis loops obtained from piezoresponse force microscopy. The faster relaxation of the tip-induced local polarization and the lower remanent state in bias-on and -off loops confirm the higher degree of ergodicity of the Na-replaced material. The difference in functional properties is attributed to small variations in chemical pressure achieved through selective doping. Raman results support this working hypothesis. [ABSTRACT FROM AUTHOR]

The stress dependence of the Raman spectrum of polycrystalline barium titanate (BaTiO3, BT) ceramics has been examined with microprobe polarized Raman spectroscopy. The angular dependence of the Raman spectrum of the tetragonal BT crystal has been theoretically established, enabling us to assess the stress dependence of selected spectral modes without the influence of crystallographic domain orientation. Upon considering the frequency shift of selected Raman modes as a function of orientation between the crystallographic axis and the polarization vector of incident and scattered light, a suitable instrumental configuration has been selected, which allowed a direct residual stress measurement according to a modified piezospectroscopic procedure. The analysis is based on the selection of mixed photostimulated spectral modes in two perpendicular angular orientations. [ABSTRACT FROM AUTHOR]

The stress dependence of the Raman spectrum of a relaxor-based polycrystalline ferroelectric lead zirconate titanate–lead nickel niobate–lead zinc niobate (PZT–PNN–PZN) has been investigated using polarized Raman microprobe spectroscopy. Emphasis has been placed on explicitly working out the second harmonic equations that relate Raman intensities to the angle between the laser polarization direction and selected crystalline axes. Based on these assessments, the effect under polarized light of crystal orientation on the intensity of selected Raman modes has been rationalized and the obtained experimental data interpreted. Raman spectra were collected with both parallel and cross polarization filters and their dependence on stress calibrated with loading the PZT–PNN–PZN samples in a four-point flexural jig. The use of polarized light allowed us to clarify the effect of domain orientation on the Raman spectrum of PZT–PNN–PZN and to perform precise calibrations of the stress dependence of the A1(TO4) Raman mode, independent of domain orientation in both poled and unpoled PZT–PNN–PZN samples. This study demonstrates the feasibility of microscopic stress (in addition to local domain orientation) evaluations in PZT materials using a polarized Raman microprobe. [ABSTRACT FROM AUTHOR]

The piezospectroscopic (PS) effect was studied in an intergrowth bismuth layer-structure ferroelectric ceramic Bi5TiNbWO15 according to a micro-Raman spectroscopic evaluation. By using a ball-on-ring flexure configuration, a biaxial stress was generated in a Bi5TiNbWO15 plate-like specimen and in situ collected Raman spectra were acquired and analyzed under several loading conditions. As the observed spectral line contained signals arising from the whole illuminated in-depth region, the laser probe information was deconvoluted (by means of an in-depth probe response function obtained according to the defocusing method) in order to deduce biaxial PS coefficients for the three Raman bands of Bi5TiNbWO15 located at 763, 857, and 886 cm-1, respectively. The biaxial PS coefficients of these bands were derived to be -1.74±0.16, -2.51±0.16, and -2.64±0.31 cm-1/GPa, respectively, and should be referred to the c axis of the Bi5TiNbWO15 crystal. [ABSTRACT FROM AUTHOR]

Ceramics in the system Ca(1-x)Nd2x/3TiO3, intended for mobile communication applications, exhibit grossly non-linear variations in microwave dielectric properties with composition. There is evidence of a structural transition and the formation of vacancies on the A-site of the perovskite structure. High density, single phase perovskite Ca(1-x)Nd2x/3TiO3 ceramics have been prepared by the mixed oxide route. Raman spectroscopy was used to investigate the structural variations, which impact on dielectric properties. The Raman spectra show that with increasing Nd content, there is a transition from an ordered structure, to a disordered arrangement of cations and vacancies, and back to an ordered arrangement in Ca0.1Nd0.6TiO3. A structural phase transition from orthorhombic Pbnm to monoclinic C2/m coincides with the order-disorder transition at Ca0.1Nd0.6TiO3. Polarized Raman spectroscopy facilitated the assignment of the Raman modes and investigation of the role of importance of domain structures. Large variation in the plane angles was attributed to differences in domain structures. Differences in the angular dependence of the Raman modes with Nd content reflect changes in the preferred orientation of the domains from lamellar twins, to wedge shaped and back to lamellar twins. [ABSTRACT FROM AUTHOR]

A quantitative assessment of c-axis oriented domains in a textured BaTiO3 (BT) single crystal has been carried out by polarized Raman microprobe spectroscopy. The relative intensity modulation of the Raman phonon modes has been theoretically modeled as a function of crystal rotation and linked to the volume fraction of c-axis oriented domains. Raman tensor elements have also been experimentally determined for the Ag and B1 vibrational modes. As an application, the internal in-plane texture and the volume fraction of c-oriented domains in the BT single crystal have been nondestructively visualized by monitoring the relative intensity of Ag and B1 Raman modes. [ABSTRACT FROM AUTHOR]

The intensity change upon crystal rotation of selected Raman modes of a lead-zirconate-titanate-based relaxor has been examined from both theoretical and experimental viewpoints. Periodic functions, representing intensity ratios between Raman bands as a function of crystal orientation, have been theoretically derived from the Raman tensor of both Ag and E phonon modes. Theoretical computations were compared with experimental data on a poled polycrystal and a discussion provided on reliability of different spectroscopic approaches for quantitative assessment of domain orientation. [ABSTRACT FROM AUTHOR]