A statistical model approximation for perovskite solid-solutions: a Raman study of lead-zirconate-titanate single crystal

Lead titanate (PbTiO3) is a classical example of a ferroelectric perovskite oxide illustrating a displacive phase transition accompanied by a softening of a symmetry-breaking mode. The underlying assumption justifying the soft-mode theory is that the crystal is macroscopically sufficiently uniform so that a meaningful free energy function can be formed. In contrast to PbTiO3, experimental studies show that the phase transition behaviour of lead-zirconate-titanate solid solution (PZT) is far more subtle. Most of the studies on the PZT system have been dedicated to ceramic or powder samples, in which case an unambiguous soft-mode study is not possible, as modes with different symmetries appear together. Our Raman scattering study on titanium-rich PZT single crystal shows that the phase transitions in PZT cannot be described by a simple soft-mode theory. In strong contrast to PbTiO3, splitting of transverse E-symmetry modes reveals that there are different locally-ordered regions. The role of crystal defects, random distribution of Ti and Zr at the B-cation site and Pb ions shifted away from their ideal positions, dictates the phase transition mechanism. A statistical model explaining the observed peak splitting and phase transformation to a complex state with spatially varying local order in the vicinity of the morphotropic phase boundary is given.Comment: Article contains four black-and-white figures, one colour figure and one Table. Symmetry analysis and details of the model are given in Appendices I and II, respectivel

Laser ablation of graphite in different buffer gases

The KrF-laser ablation of graphite into 300 Torr of He, Ne, Ar, and Xe has been studied by fast imaging of the plasma emission and post-deposition analyses of collected film deposits. In each case, the soot which was redeposited on the irradiated rod following ablation was highly fullerene-deficient compared to the material collected on the sample disk 1.5 cm from the rod, as determined by laser desorption Fourier Transform Mass Spectrometry (FTMS) Investigation of the plasma plume propagation using fast ICCD photography reveals three main phases to the expansion: (1) forward motion, deceleration and stopping of the leading edge of the plume, (2) an apparent reflected shock within the plume which propagates backward and reflects from the rod surface, (3) coalescence of these two components, resulting in continued expansion and dissipation of the plasma and the appearance of glowing ultrafine particles. For the laser plume propagating in 300 Torr of Xe the characteristic time intervals for these three phases are 0-300 ns, 300-1000 ns, and 1-1000 {mu}s for phases (1), (2), and (3) respectively. The possible explanation of the observed difference in fullerene content is discussed on the basis of different plasma phases resulting in soot deposition on the rod and sample disk. The measurement of ro-vibrational spectra of electronically excited C{sub 2} has been performed. Rotational and vibrational temperatures, T{sub R} = 3000 {+-} 300K and T{sub V} = 6000 {+-} 500K have been obtained from the comparison of measured and calculated C{sub 2} -Swan band emission

Samarium-Activated La2Hf2O7 Nanoparticles as Multifunctional Phosphors

Recent developments in the field of designing novel nanostructures with various functionalities have pushed the scientific world to design and develop high-quality nanomaterials with multifunctional applications. Here, we propose a new kind of doped metal oxide pyrochlore nanostructure for solid-state phosphor, X-ray scintillator, and optical thermometry. The developed samarium-activated La2Hf2O7 (LHOS) nanoparticles (NPs) emit a narrow and stable red emission with lower color temperature and adequate critical distance under near-UV and X-ray excitations. When the LHOS NPs are exposed to an energetic X-ray beam, the Sm3+ ions situated at the symmetric environment get excited along with those located at the asymmetric environment, which results in a low asymmetry ratio of Sm3+ under radioluminescence compared to photoluminescence. High activation energy and adequate thermal sensitivity of the LHOS NPs highlight their potential as a thermal sensor. Our results indicate that these Sm3+-activated La2Hf2O7 NPs can serve as a multifunctional UV, X-ray, and thermographic phosphor