Temperature and composition dependence of vibrational modes in Sm1−xLaxAlO3

At room temperature and for x₀ ～ 0.43, the system Sm_1?xLa_xAlO₃ undergoes a first order phase transition in which an orthorhombic structure transforms into a rhomboedral structure as x increases. This phase transition was investigated by Raman scattering experiments on polycrystalline compounds in the range 0 ? x ? 1. The dependence of low frequency modes on x is reported and compared with their well known temperature dependence. Soft modes have been observed in the orthorhombic (D_2h¹⁶) and rhomboedral (D_3d⁶) phases. It was found that the first order phase transition is probably driven by a double degenerate mode whose two components in the low symmetry phase display a linear composition dependence of their squared frequencies. The source of anomalous behaviour of Raman bands near the phase transition is discussed.     

Raman spectroscopic study of the lattice dynamics in the Rb2KMoO3F3 oxyfluoride

The lattice dynamics of the Rb₂KMoO₃F₃ oxyfluoride has been studied by Raman spectroscopy in the temperature range 7–400 K. A phase transition has been revealed at T ≈ 185 K with decreasing temperature. Anomalies of the frequencies and Raman line half-widths have been analyzed. No condensation of soft lattice modes has been found. The character of changes in the Raman spectra of the Rb₂KMoO₃F₃ oxyfluoride shows that the phase transition is related to variations in the [MoO₃F₃]^3? molecular octahedron.     

New phase transition in LiKSO4

A subtle first order phase transition in LiKSO₄ has been discovered with the help of a temperature dependent study of the Raman intensity measurements of certain polar modes in different polarization configurations. The room temperature hexagonal C⁶₆ (P6₃) phase transforms to trigonal C⁴_3v (P31c) phase at 201°K while cooling; the reverse transformation (on heating) takes place at 242°K. The phase transition appears to be primarily associated with a cooperative reorientation of SO₄ tetrahedra in the crystal.     

Infrared lattice vibration spectra of tetragonal ZnP2

Infrared reflectivity spectra of tetragonal ZnP₂ are measured in the frequency range from 40 to 600 cm^-1 for both polarization directions E ⊥ c and E 6 c. The parameters of 9 E modes and 4 A₂ modes are determined by a dispersion analysis of the spectra. Three additional A₂ modes are detected by infrared transmission measurements. The results obtained are compared with previous Raman scattering and two-phonon combination mode spectra.     

Optic-mode coupling in ferroelectric gadolinium molybdate

Separate measurements of the A₁(TO) and A₁(LO) Raman spectra of ferroelectric gadolinium molybdate at 80°K and above have elucidated the origin of the anomalous temperature dependence of the two lowest frequency lines in the A₁(TO) spectrum. The observed behavior is postulated to be the result of coupling among modes at 44.5, 51.5, and 83 cm^?1 (at 80°K). The 44.5 and 83 cm^?1 modes become the degenerate, soft zone-boundary modes of the paraelectric phase while the 51.5 cm^?1 mode changes to B₂ symmetry. The two lowest frequency lines are the same as those observed previously in i.r. absorption.     

A Raman and dielectric study of a diffuse phase transition in (Pb<Subscript>1-x</Subscript>Ca<Subscript>x</Subscript>)TiO<Subscript>3</Subscript> thin films

Dielectric and Raman scattering experiments were performed on polycrystalline Pb_1-xCa_xTiO₃ thin films (x=0.10, 0.20, 0.30, and 0.40) as a function of temperature. The results showed no shift in the dielectric constant (K) maxima, a broadening with frequency, and a linear dependence of the transition temperature on increasing Ca²⁺ content. On the other hand, a diffuse-type phase transition was observed upon transforming from the cubic paraelectric to the tetragonal ferroelectric phase in all thin films. The temperature dependence of Raman scattering spectra was investigated through the ferroelectric phase transition. The temperature dependence of the phonon frequencies was used to characterize the phase transitions. Raman modes persisted above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the local cubic symmetry due to chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands in some temperature interval above the FE–PE phase transition temperature suggested a diffuse-type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. PACS 77.80.Bh; 77.55.+f; 78.30.-j; 77.80.-e; 68.55.-a     

Raman scattering investigation of ferroelastic Sb5O7I crystals

Sb₅O₇I undergoes a displacive phase transition at 481 K where the symmetry is changed fromC _6h ² toC _2h ⁵ . In the low temperature monoclinic phase the crystal is ferroelastic. The polarized Raman spectra of Sb₅O₇I have been measured at various temperatures below and above the phase transition. The frequencies and symmetries of most of the theoretically expected Raman active phonons in the ferroelastic phase have been determined. The observation of a soft mode in the ferroelastic phase which disappears above the phase transition together with the fact that the unit cell of the ferroelastic phase is twice as large as that of the paraelastic structure permits the conclusion that the phase transition results from a phonon instability at the Brillouin zone boundaryM-point of the hexagonal phase. The temperature dependent splittings and intensity changes of several Raman lines are discussed with respect to the ferroelastic property of the crystal and the phase transition.     

Leakage current, ferroelectric and structural properties in Pb1−xBaxTiO3 thin films prepared by chemical route

Single-phase perovskite structure Pb_1−xBa_xTiO₃ thin films (x=0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO₂/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively.     

Raman and infrared spectra of CdIn2S4 and ZnIn2S4

Four one-phonon Raman lines have been found in CdIn₂S₄ (ZnIn₂S₄) spinels at 92 (72) cm^-1, 186 (184) cm^-1, 246 (253) cm^-1, and 367 (372) cm^-1 for incident photon energies well below the energy gap E_G ～ 2.4 (2.2) eV at 300 K. For photon energies close to E_G, the 367 cm^-1 mode underwent a resonant enhancement in CdIn₂S₄ and four infrared active but Raman forbidden F_1u modes appeared in the CdIn₂S₄ and ZnIn₂S₄ Raman spectra: TO modes at 226 (221) cm^-1 and 309 (312) cm^-1, and LO modes at 274 (272) cm^-1 and 340 (342) cm^-1.     

Phase transitions in PbZr0.72Sn0.28O3 single crystals studied by Raman spectroscopy

ABSTRACT

Raman light scattering measurements in the temperature range from 80 to 830 K were performed on a PbZr_0.72Sn_0.28O₃ single crystal. The frequencies of the Raman lines were analyzed and discussed in terms of the sequence of structural phase transitions. It was found that Raman spectrum displays important changes near 440, 480 and 493 K. The incorporation of more than 25 mol% of Sn⁴⁺ ions into the structure of PbZrO₃ enhances polar fluctuations above T_C as compared to the less Sn-doped crystals. These fluctuations lead to appearance of a ferroelastic intermediate phase below T_C. It is demonstrated that the structural phase transformation in PbZr_0.72Sn_0.28O₃ can be considered as the result of softening of a number of modes.     

Soft vibrational mode in LiNbO3 and LiTaO3

The temperature dependence of the far-infrared reflectivity as obtained with a scanning interferometer for the A₁- and E-type modes of both LiNbO₃ and LiTaO₃ is reported in the ferroelectric phase. Results of a Kramers-Kronig analysis are compared with Raman and neutron scattering data which are controversial about the existence of a soft vibrational mode. For LiTaO₃, spectra are obtained 300 K above the Curie temperature, in the paraelectric phase. The lowest-frequency A₁ (TO) mode is unambiguously found as soft and becomes rapidly overdamped.     

Effects of the phase transition in Hg2(Br,I)2 crystals

The effects of the phase transition in Hg₂(Br,I)₂ crystals have been investigated over a wide range of temperatures by the Raman scattering spectroscopy and X-ray diffraction analysis. The overtones (at the X point of the Brillouin zone boundary) and the fundamental tones (at the center of Brillouin zone) of soft modes are found in the Raman spectra of these crystals and studied in detail. The density of one-phonon states of the soft TA branch manifests itself in the Raman spectra of mixed crystals. The potentialities of the soft-mode spectroscopy are realized in full measure. Analysis of the ratio between intensities of overtones and fundamental tones of the soft modes has demonstrated the applicability of the Landau phenomenological theory of phase transitions. The orthorhombic splitting of the reflections corresponding to the basal plane is revealed in the X-ray diffraction patterns and thoroughly explored. The temperature dependences of the isotropic and shear spontaneous strains are obtained. It is shown that the shear spontaneous strain plays a decisive role. The critical indices are determined and the model of the improper ferroelastic phase transition D _4h ¹⁷ → D _2h ¹⁷ in the vicinity of the tricritical point is corroborated.     

Raman study of charge-density-wave phase transition in quasi-one-dimensional conductor (TaSe4)2I

Polarized Raman spectra were obtained in the quasi-one-dimensional conductor (TaSe₄)₂I above and below the charge-density-wave (CDW) transition temperature (T_c=263 K). The Raman intensities of many peaks become intenser and two of the phonon peaks shift to higher frequency with decreasing temperature. Moreover a new broad peak at about 90 cm^?1 and a new peak around 166 cm^?1 appear in the low-temperature phase. The polarization characteristic shows that the former is assigned to totally symmetric mode. The damping constant of the phonon at 90 cm^?1 increases markedly with increasing temperature. The frequency shifts to higher frequency as the temperature increases and the coupling coefficient is approximately proportional to (T_c?T)^{$\text{1}\text{2}$}. This peak becomes Raman active owing to the CDW phase transition. The temperature dependence of the damping constant and the frequency shift may have a relation to the dynamical properties of the CDW phase transition.     

New N2+Electronic States in the Region of 23–28 eV

Threshold photoelectron spectra of N₂⁺were measured between 23.4 and 27.6 eV with high resolution and high intensity by using the penetrating field technique and synchrotron radiation. Five vibrational progressions were observed. The first of these progressions was theC²Σ_u⁺state. The second progression was identified as the transition to the second state of²Π_gsymmetry found by P. Baltzer, M. Larsson, L. Karlsson, B. Wannberg, and M. Carlsson (1992.Phys. Rev. A46,5545). The third progression, which was discovered by F. Merkt and P. M. Guyon (1993.J. Chem. Phys.99,3400), can be designated as the²Σ_u⁻state by comparison with previous theoretical study (E. W. Thulstrup and A. Andersen, 1975.J. Phys. B8,965). The fourth and fifth progressions were designated as the²Δ_uand 2²Π_ustates by similar comparison with previous theories.     

Role of the TiO6 octahedra on the ferroelectric and piezoelectric behaviour of the poled PbMg1/3Nb2/3O3-xPbTiO3 (PMN-PT) single crystal and textured ceramic

Field cooling (FC) poled/unpoled PMN-29%PT single crystal and room temperature (RT) poled/unpoled PMN-34.5%PT textured ceramic were investigated between ∼0 and 300 °C by thermal expansion, dielectric and Raman spectroscopy. New phase transitions are evidenced at 40, 91 and 180 °C in the case of FC PMN-29%PT as well as at 70 and 200 °C for RT PMN-34.5%PT and their order is discussed. The physical properties of the textured ceramics are rather similar to the ones observed for the single crystals that make them low-cost alternative for a wide range of applications. However, the temperatures and character of the phase transitions strongly depend on the kind of the poling conditions. Temperature dependences of the Raman line parameters show that the NbO₆ octahedra remain stable during temperature increase, while TiO₆ ones evolve quasi-continuously. The step transitions of the Pb²⁺ ion sublattice are evidenced. This suggests that the TiO₆ and Pb²⁺ sublattices are especially coupled. The role of the TiO₆ clusters on the structural phase transitions and dielectric properties of the PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-PT) system is discussed. The presence of the Raman modes above the maximum dielectric permittivity reveals that the local symmetry is lower than the cubic one (Pm3m). The decrease of the Raman line intensities vs. temperature indicates precisely the continuous evolution of the local symmetry towards the cubic one. The temperature evolution of the Rayleigh wing parameters appears sensitive to the phase transitions’ presence.     

Electron hopping and optic phonons in Eu3S4

Raman scattering on single crystals of Eu₃S₄ does not show the allowed q=o phonon modes in the cubic phase and exhibits no new modes in the distorted low temperature phase (T<186 K). Above the Curie temperature T_c=3.8 K the scattering is dominated by a spin-disorder induced one-phonon density of states allowing for the observation of the zone boundary phonon breathing mode of the S^2?ions. This mode does not show any anomaly near the charge order -disorder phase transition T_t=186 K. Temperature tunable spin fluctuations associated with the temperature activated Eu²⁺→Eu³⁺ electron hopping are detected in the scattering intensity, superimposed on the usual thermal spin disorder.     

Probing the ferroelectric phase transition in sol–gel‐derived polycrystalline bismuth ferrite thin films

Polycrystalline BiFeO₃ (BFO) thin films were successfully grown on Pt/Ti/SiO₂/Si(100) and SrTiO₃ (STO) (100) substrates using the chemical solution deposition (CSD) technique. X‐ray diffraction (XRD) patterns indicate the polycrystalline nature of the films with rhombohedrally distorted perovskite crystal structure. Differential thermal analysis (DTA) was performed on the sol–gel‐derived powder to countercheck the crystal structure, ferroelectric (FE) to paraelectric (PE) phase transition, and melting point of bismuth ferrite. We observed a significant exothermic peak at 840 °C in DTA graphs, which corresponds to an FE–PE phase transition. Raman spectroscopy studies were carried out on BFO thin films prepared on both the substrates over a wide range of temperature. The room‐temperature unpolarized Raman spectra of BFO thin films indicate the presence of 13 Raman active modes, of which five strong modes were in the low‐wavenumber region and eight weak Raman active modes above 250 cm⁻¹. We observed slight shifts in the lower wavenumbers towards lower values with increase in temperature. The temperature‐dependent Raman spectra indicate a complete disappearance of all Raman active modes at 840 °C corresponding to the FE–PE phase transitions. There is no evidence of soft mode phonons. Copyright © 2008 John Wiley & Sons, Ltd.     

I.R. Lattice-vibration spectra of MnF2

The room temperature reflectivity of MnF₂ has been measured in the far i.r. between 50 and 800 cm^?1. The reflectivity spectra show four i.r.-active modes which can be identified as E_u and A_2u modes. The spectra also show structure which might be related to multiphonon effects. The dielectric functions were determined by fitting the reflectivity data with classical oscillator parameters.     

The temperature dependence of the Raman spectra of chromium‐doped titanite (CaTiOSiO4)

The temperature dependence of the Raman bands of Cr⁴⁺ modes which show enhanced intensities due to pre‐resonance effects is reported from 293 to 673 K in chromium‐doped titanite (CaTiOSiO₄). Some aspects of the temperature dependence of Raman bands in pure, synthetic titanite which have not been previously published are also included in this study. Two Raman‐active components of A_g and B_g symmetry, respectively, of the symmetric Si–O mode in titanite are predicted under P2₁/a symmetry and also been identified in this phase for the first time. The one component of B_g symmetry disappears just above the antiferroelectric–paraelectric transition at ~500 K in accordance with the predictions under A2/a symmetry for the high‐temperature phase. Two resonance‐enhanced components of the Cr⁴⁺–O stretch are also evident in the P2₁/a phase and only one could be identified in the A2/a phase, again in accordance with group‐theoretical predictions. These observations can be used to characterize the P2₁/a and A2/a phases of pure synthetic and chromium‐doped titanite. The temperature dependence of the Cr⁴⁺–O modes can be approximated by two‐dimensional Ising behavior with the critical exponent β ≈ 1/8 below 450 K. Between 450 and 498 K, anomalous behavior is observed and this could be due to the appearance of mobile anti‐phase boundaries (APBs). Anomalous behavior also persists to temperatures above 500 K. The half‐width of the Ti–O stretching mode reflects the influence of the order parameter (Ti–O displacements) as well as mobile anti‐phase boundaries. No evidence could be found of the existence of other ions such as Cr⁴⁺‐ions in Ti‐sites and/or Cr³⁺‐ions also in Ti‐positions in Cr‐doped titanite in the Raman spectra using different laser lines to excite the spectra. Copyright © 2013 John Wiley & Sons, Ltd.     

Central peak in the strontium titanate crystal near the tetragonal-to-cubic phase transition

Raman spectra of the SrTiO3 crystal have been measured in wide temperature (22?C316 K) and frequency (2?C1020 cm^?1) ranges. It has been shown that a central peak appears in low-frequency Raman spectra at temperatures above 70 K. In the spectral geometry with polarization rotation near the temperature T _c = 106 K of the cubic-to-tetragonal phase transition, the central peak exhibits properties of the order-disorder phase transition. Such a behavior of the central peak has been explained by the interaction of the low-frequency soft mode E _g with the relaxation mode near T _c .