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.     

Enhancement of the superconducting transition temperature near a phase instability in NaxWO3

The superconducting transition temperature of tetragonal I sodium tungsten bronze (Na_xWO₃) has been found to increase rapidly as the x-value is decreased to the metal-semiconductor phase transition. It is suggested that a soft mode instability is responsible for the increased electron-phonon interaction near the phase transition.     

Raman scattering from GaSe1−xTex

The long-wavelength optical phonons of the layer GaSe_1?xTe_x have been investigated at room temperature by means of Raman scattering spectroscopy. The spectra of the Bridgman grown crystals were excited with the 1,06 μm line of the continuously operated YAG:Nd³⁺ laser. Detailed study of the Raman spectra of GaSe_1?xTe_x solid solutions showed that there is an abrupt change in the frequency-composition dependences for all observed modes. It is shown, that a phase transition from hexagonal ?-GaSe to monoclinic GaTe in GaSe_1?xTe_x solid solutions takes place in the composition range 0.27 ? × ? 0.72. Only one mode behaviour of the optical phonons was observed in GaSe_1?xTe_x system.     

A comment on the phase transition in RbCaF3

The structural phase transition in RbCaF₃ has been examined by observing super lattice points by means of neutron diffraction. There is one structural phase transition with the R₂₅^x soft mode phonon condensation up to 4.2 K. The rotation angle of CaF₆ octahedra, Ø, is calculated as 8.64 degrees at 60 K. The temperature dependence of Ø is also given.     

‘Soft’ optical phonons and the morphotropic phase transition of the Pb(Ti1−x, Zrx)O3 system

Room temperature Raman scattering results for the Pb(Ti_1?x, Zr_x)O₃ system in its tetragonal ferroelectric phase are analyzed. For x ≤ 0.25, the square of the frequency of the ‘soft’ E(TO) phonon is linear in the Zr concentration. In addition, we find that the morphotropic phase transition at x = 0.535 may be associated with an instability of this ‘soft’ phonon. It is shown that changes in the short-range harmonic forces play an important role in the x-dependence of the ‘soft’ E(TO) phonon frequency.     

Spin glass phase transition in Hg1−kMnkTe semimagnetic semiconductors

Low field interband Faraday rotation and a.c. magnetic susceptibility are investigated in Hg_1?kMn_kTe and Hg_1?k?xMn_kTe semimagnetic semiconductors (k?0.5). The spin glass phase transition is experimentally manifested by characteristic cusps in χ(T) and kinks in θ(T). The transition temperatures obtained from both types of experiments are well correlated which enable us to determine the phase diagram for Hg_1?kMn_kTe system. The spin glass phase transition occurs at low temperature in quaternary alloys than in Hg_1?kMn_kTe alloys with identical Mn composition. This implies that the antiferromagnetic interaction between Mn²⁺ ions due to the virtual valence to conduction band transitions plays a significant role in the mechanism responsible for the spin glass formation.     

The suppression of structural phase transformation in LaVO3 and La1−xSrxVO3 thin films fabricated by pulsed laser deposition

Highly oriented (100) thin films of LaVO₃ and La_1−xSr_xVO₃ have been fabricated by pulsed laser deposition in a reducing atmosphere. The films show a transition from insulating to metallic behaviour in the composition region of x, 0.175<x<0.200. In the single crystals of the antiferromagnetic insulating phase, a first-order structural phase transition is observed few degrees below the magnetic transition, which manifests itself as a kink in the temperature dependence of resistivity. In the highly oriented thin films of LaVO₃ and La_1−xSr_xVO₃ fabricated on lattice matched substrates in this study, the structural phase transformation in the insulating phase has been suppressed. The electrical conduction is found to take place via hopping through localized states at low temperatures. The metallic compositions show a non-linear (T^1.5) behaviour in the temperature dependence of resistivity. V (2p) core level spectra of these films show a gradual change in the relative intensities of V³⁺ and V⁴⁺ ions as the value of x increases.     

Raman scattering from soft phonons in NdP5O14

Raman spectra of NdP₅O₁₄ were recorded between 4.2 and 600 K and analyzed. The monoclinic-orthorhombic phase transition temperature was determined to be 420 K by measuring the energy of an A_g-B_2g and a B_g-B_3g soft optic phonon mode as a function of temperature (symmetries refer to the monoclinic and orthorhombic phase, respectively). Coupling of these optic phonons to the soft acoustical phonon which is associated with the phase transition is discussed.     

Symmetry and lattice-dynamic aspects of structural phase transitions in (CH3NH3)2MnCL4 and related compounds

A group theoretical analysis of the second-order structural phase transition in (CH₃NH₃)₂MnCL₄ at 394°K and of similar transitions in ethyl and propyl compounds (D¹⁷_4h→D¹⁸_2h) was performed. The soft mode transforms according to the τ^x₅-irreducible representation at the X-point of the Brillouin-zone boundary and its eigenvector is discussed. The transition is of the order-disorder type and is caused by a slowing down of the hindered rotation of NH₃-groups. Knowing the symmetry of the order parameter, a thermodynamic potential expansion was constructed and expected anomalies in material constants around the transition temperature are briefly discussed. The high temperature phase transitions in analogous copper compounds are explained as a sequence D¹⁷_4h→D¹⁸_2h→D¹⁵_2h. The second of these phase transitions is driven by a soft mode transforming as the τ^Y₇-representation at the D¹⁸_2h Brillouin zone boundary.     

Observation of soft-modes in a single crystal of Rb2ZnBr4 by Raman scattering

The Raman spectra of an oriented single crystal of Rb₂ZnBr₄ shows three soft modes. One of them is interpreted as the amplitude mode of the incommensurate phase. The second one, seen well below the lock-in transition temperature appears as the phase mode. Moreover, an additional soft mode is observed between T=120 K and T=20 K, in the b(c, c)a scattering geometry. By extrapolation it is found that its frequency would vanish around T₃=140 K ± 10 K. This soft mode is likely to be related to a new phase transition.     

Phase separation, ferromagnetism and magnetic irreversibility in La1−xSrxMn1−yFeyO3

Magnetic susceptibility, χ(T), is investigated in ceramic La_1−xSr_xMn_1−yFe_yO₃ (LSMFO) samples with x=0.3 and y=0.15−0.25. A ferromagnetic (FM) transition observed in LSMFO is accompanied with an appreciable decrease of the transition temperature with increasing y, which is connected to breaking of the FM double-exchange interaction by doping with Fe. Strong magnetic irreversibility, observed in low (B=10 G) field, gives evidence for frustration of the magnetic state of LSMFO. The FM transition, which is expanded with increasing B, is more pronounced in the samples with y=0.15-0.20 and broadens considerably at y=0.25, where the irreversibility is increased. Well above the transition, χ(T) exhibits a Curie-Weiss asymptotic behavior, yielding very large values of the effective Bohr magneton number per magnetic ion, incompatible with those of Mn or Fe single ions. At y=0.15 and 0.20 a critical behavior of χ⁻¹(T)∼(T/T_C−1)^γ in the region of the FM transition is characterized by influence of two different magnetic systems, a 3D percolative one with γ₌γ_p≈1.8 and T_C=T_C^(p), and a non-percolative 3D Heisenberg spin system, with γ=γ_H≈1.4 and T_C=T_C^(H), where T_C^(p)<T_C^(H). At y=0.25 the percolative contribution to the critical behavior of χ(T) is not observed. The dependence of χ on T and y gives evidence for phase separation, with onset already near the room temperature, leading to generation of nanosize FM particles in the paramagnetic host matrix of LSMFO. The ferromagnetism of LSMFO is attributable to percolation over the system of such particles and generation of large FM clusters, whereas the frustration is governed presumably by a system of smaller weakly-correlated magnetic units, which do not enter the percolative FM clusters.     

Elastic properties of the RIV-RIII rotator phases of alkanes

A model free energy has been constructed to describe the R_IV-R_III rotator phase transition in alkanes in terms of the elastic strains and order parameter. The conditions for the R_IV-R_III phase transition are discussed. From the free energy, the order parameter and the elastic strains are determined. The model free energy describes the first or second order character of the R_IV-R_III transition depending on the strength of the coupling. The elastic properties in the vicinity of the R_IV-R_III transition are discussed on the basis of a free energy expansion. The temperature dependence of the elastic constants is calculated on both sides of the transition. The coupling between the order parameter and elastic stains is shown to have a crucial influence on the phase behavior and the order of the transition.     

Structural and magnetic studies of the alloy system GdInxAg1-x

The structural and magnetic studies below room temperature of the alloy system GdIn_xAg_1-x(0?x?1) are reported. It has been found that alloys with x?0.5 crystallize in CsCl type cubic structure, but the distortion of the unit cell starts for alloys with x#62;0.5 and for these alloys the unit cell becomes tetragonal. No phase change is evident from the low temperature (295-8 K) structural studies. However, a break appears in the X^-1_m vs. T linear plot of each alloy of this system at a specific temperature (designated as break temperature T_B). The variation of T_B with x is similar to the variation of phase transition temperature with x reported for LaIn_xAg_1-x. Close agreement has been found in the values of effective magneton number (p), magnetic ordering [Néel (T_N) or Curie (T_C)] and paramagnetic Curie (θ_p) temperature for materials studied by us and earlier workers. The variation of magnetization with applied field strength (2.5-65)×10⁵ Am^-1) at 4.2 K has also been reported for ferromagnetic of this system. It has been concluded that alloys with 0.4?x?0.6 are simple ferromagnets with parallel alignment of magnetic moment in the ground state. The angular arrangement of the magnetic moment starts appearing in the ground state for alloys with x?0.4 for x#62;0.6 and continues till x becomes closure to 0.17 or 0.84. The alloys with x=0.17 or x=0.84 have θ_p and T_C equal to zero and appear paramagnetic. Angular arrangement in spins again appear for alloys with x?0.17 or x#62;0.84, however all materials with 0?x?0.17 or 0.84?x?1 remain antiferromagnetic.     

Perturbed angular correlation study of Ta-doped PbTi1−xHfxO3 compounds

In this work, the hyperfine quadrupole interaction at Ta-doped PbTi_1−xHf_xO₃ polycrystalline samples is studied for the first time. Powders with x=0.25, 0.50 and 0.75 were prepared and characterized by X-ray diffraction analysis. Perturbed Angular Correlation (PAC) analyses were done as a function of temperature, using low concentration ¹⁸¹Ta nuclei as probes. In the ferroelectric and paraelectric phases of these compounds two sites were occupied by the probes. For each site the quadrupole frequency, asymmetry and relative distribution width parameters were obtained as a function of temperature above and below the Curie temperature (T_C). One of these sites was assigned to the regular Ti–Hf site, while the other one was assigned to some kind of defect. The behavior of the hyperfine parameters as a function of temperature was analyzed in terms of a recent published phase diagram and the presence of disorder below and above T_C. For the three compositions measured, the obtained hyperfine parameters present discontinuities which correspond to the ferroelectric–paraelectric phase transition. In both phases it was found broad frequency distributed interactions. The disorder in the electronic distribution would be responsible for the broad line width of the hyperfine interaction.     

Magnetic susceptibility anomaly connected with a displacive phase transition in MnAs1−xPx and CrxMn1−xas compounds

With the second order B31 [rlhar2] B8₁ phase transition T_t in MnAs_1-xP_x and Cr_xMn_1-xAs compounds a high-spi low-spin transition occurs simultaneously with a drastic change in the magnetic coupling. An interpolation scheme is proposed which yields C and T_c for each temperature below T_t separately.     

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 .     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

Temperature-dependence of the structural and afterglow luminance properties of polymer/SrAlxOy:Eu,Dy composites

Although aluminate phosphors have attracted great interest for applications in lamps, cathode ray tubes and plasma display panels, there still remain issues affecting operational parameters such as luminescence efficiency, stability against temperature, high color purity and perfect decay time. In addition, issues involving important aspects of the monoclinic↔hexagonal phase transition temperature still exist. In this work, SrAl_xO_y:Eu²⁺,Dy³⁺ phosphor powders were prepared by the sol–gel method. X-ray diffraction (XRD) has shown that both crystallinity and crystallite sizes increased as the temperature increased. Both SrAl₂O₄ and Sr₂Al₃O₆ phases were observed. Photoluminescence (PL) characterization shows temperature-dependence, which indicates emission at low and high annealing temperatures originating from Eu²⁺ and Eu³⁺ ions. Thermoluminescence glow and decay measurements provided useful insight on the influence of traps on luminescence behavior. Differential scanning calorimetry (DSC) and thermogravimetric studies (TGA) on composites of the phosphor in low density polyethylene (LDPE) demonstrated the varied influence of annealing temperature on some luminescence and thermal properties.     

Study of the CulCu2S system. conductivity of the solid solution Cu1+xI1−xSx(x<0.5)

A structural study of the CuICu₂S system has shown that a large solid solution ranges from pure CuI to Cu₃SI with a regular decrease of tehcell parameter ($\text{a=6.045 to 5.901}\text{A}\text{?}$); for richer Cu₂S concentrations, two-phase systems appear with the formation of a new Cu₇S₃I compound, and another solid solution exists for higher Cu₃S fractions (0.85<x<1). The ionic conductivity of the solid solution Cu_1+xI_1?xS_x (x<0.5) has been measured as a function of temperature between 54 and 307°C. The conductivity increases from 10^?7 ω^?1 cm^?1 (CuI) to 10^?3 ω^?1 cm^?1 (Cu_1.4I_0.6 S_0.4) at 25°C and then decreases until 10^?4 ω^?1 cm^?1 (Cu₃SI). In this last domain, no further phase transition occurs below the melting point and the low temperature γ phase can be considered as a stabilization of the high-conducting α phase. The variations of the conductivity are directly connected to those of the activation energy that decreases to a minimum value of 2.5 kcal mole^?1 for Cu_1.4I_0.6S_0.4.     

Synthesis and ferroelectric properties of bismuth layer-structured (Bi7−xSrx)(Fe3−xTi3+x)O21 solid solutions

Bismuth layer-structured (Bi_7−xSr_x)(Fe_3−xTi_3+x)O₂₁ (BSFT) ceramics were synthesized and the ferroelectric properties and crystal structure were investigated. X-ray powder diffraction profiles and refinement of the lattice parameters indicated single phase BSFT was obtained in the composition range 0-1.5. The lattice parameter b of BSFT remained almost constant, while a slight decrease in the lattice parameter a was observed by the Sr and Ti substitution for Bi and Fe, respectively, which indicated an increase in the orthorhombicity. The dependence of the BSFT lattice parameter on temperature implied a phase transition from the orthorhombic to the tetragonal phase, which was in good agreement with the Curie temperature. The remnant polarization P_r, of BSFT was significantly improved by the Sr and Ti substitution for Bi and Fe, and ranged from 9 to 16 μC/cm², although no remarkable variation in the coercive field E_c was observed. As a result, a well-saturated P-E hysteresis loop of BSFT ceramic was obtained at x=0.5 with a P_r of 30 μC/cm at an applied voltage of 280 kV/cm.