RESUMO
Polarized Raman, IR, and time-domain THz spectroscopy of orthorhombic lead zirconate single crystals have yielded a comprehensive picture of temperature-dependent quasiharmonic frequencies of its low-frequency phonon modes. It is argued that these modes primarily involve vibrations of Pb ions and librations of oxygen octahedra. Their relation to 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. Analysis of the results yields insight into the phase transition mechanism, involving a soft ferroelectric branch coupled by a trilinear term to another two oxygen octahedra tilt modes.
RESUMO
Dielectric properties of Eu(0.5)Ba(0.5)TiO(3) ceramics were investigated between 10 and 300 K in the frequency range of 1 MHz-100 THz. Permittivity exhibits a strong peak near the ferroelectric phase transition at 215 K. This is mainly due to softening of the lowest frequency polar phonon revealed in THz and infrared spectra. Dielectric relaxation was observed also below the ferroelectric soft mode frequency in the whole investigated temperature region, but it is probably caused by some defects such as Eu(3 + ) cations or oxygen vacancies. This implies that the ferroelectric phase transition has predominantly a displacive character. Raman scattering spectra revealed a lowering of crystal symmetry in the ferroelectric phase and XRD analysis indicated orthorhombic A2mm symmetry below 215 K. The magnetic measurements performed at various frequencies in the field cooled and field heating regime after cooling in zero magnetic fields excluded spin glass behavior and proved an antiferromagnetic order below 1.9 K in Eu(0.5)Ba(0.5)TiO(3).
Assuntos
Compostos de Bário/química , Cerâmica/química , Európio/química , Compostos Férricos/química , Magnetismo , Titânio/química , Condutividade Elétrica , TemperaturaRESUMO
The paper proposes a fully optical method for determination of a cubic crystal grain orientation in a sample inspected by a Raman microscope. The method is based on a universal and strong polarisation anisotropy of the Raman scattering by doubly degenerate optic phonon modes and it only requires a standard Raman microscope equipped with a polarisation analysis. Explicit formulas for the orientation of the crystal grain are derived. The feasibility of the approach is demonstrated by comparing grain orientations in a polycrystalline cubic lacunar spinel GaV4S8 determined independently using electron backscatter diffraction and Raman scattering methods.
RESUMO
Sodium niobate (NaNbO3, or NNO) is known to be antiferroelectric at temperatures between 45 and 753 K. Here we show experimentally the presence of the ferroelectric phase at temperatures between 100 and 830 K in the NNO crystals obtained by top-seeded solution growth. The ferroelectric phase and new phase transitions are evidenced using a combination of thermo-optical studies by variable angle spectroscopic ellipsometry, Raman spectroscopy analysis, and photoelectron emission microscopy. The possibility for strain-induced ferroelectricity in NNO is suggested.
Assuntos
Cristalização/métodos , Campos Magnéticos , Nióbio/química , Sódio/química , Teste de Materiais , Conformação Molecular , Transição de FaseRESUMO
The lattice dynamics of La(1/2)Na(1/2)TiO(3) single crystal have been investigated by far-infrared and Raman scattering spectroscopy. Far-IR reflectivity spectra revealed Slater, Last and Axe modes near 140, 190 and 555 cm(-1), respectively. The frequency of the Slater mode decreases by about 10% on cooling, which is enough to account for the observed increase of the low-frequency permittivity. The results allowed us to discuss the reasons for the suppressed ferroelectricity of the material. Temperature evolution of the Raman scattering intensity of an oxygen octahedra bending mode near 455 cm(-1) suggests a second-order phase transition towards the perovskite aristotype phase near 870 K.
Assuntos
Compostos de Cálcio/química , Lantânio/química , Óxidos/química , Sódio/química , Espectrofotometria Infravermelho , Análise Espectral Raman , Titânio/química , Modelos Moleculares , Estrutura Molecular , Transição de Fase , Temperatura , TermodinâmicaRESUMO
This study reports the preparation of thin nanoparticulate films of titanium dioxide and its modified version doped with a transition metal. The behavior of prepared films was described by means of their photocatalytic and photo-induced electrochemical properties. The TiO(2) and M/TiO(2) (M=Ag, Zr, Fe) thin films were produced via a standard sol-gel method using titanium n-butoxide, acetylacetone, and transition metal acetylacetonates as precursors. Prepared films were analyzed by a series of techniques involving XRD, Raman spectroscopy, SEM, AFM, and XPS. Their photocatalytic activity was monitored with the aid of decomposition of the model compound Rhodamine B in water. All films were then tested for their photo-induced electrochemical properties based on evaluation of polarization curves (photocurrents). The highest reaction rate constant (0.0101min(-1)), which was even higher than that for pure TiO(2), was obtained for the Ag/TiO(2) sample. The highest quantum yield of the charge collection was determined for the undoped TiO(2) film.