Synchrotron X-ray diffraction studies on the phase transitions in the spinel LixMn3−xO4 intercalation compounds

Detailed investigations have been undertaken of the lithium for manganese substitution effect on the LiMn₂O₄, in the system Li_xMn_3−xO₄, for 0.95≤x≤1.05, that is for the nearly stoichiometric lithium content. Synchrotron X-ray measurements have been performed in the temperature range 10–300 K. The diffraction experiments were carried out at the DESY-HASYLAB high-resolution powder diffractometer (beamline B2), equipped with a closed-cycle He-cryostat. Very small changes in the lithium content influence clearly the low-temperature crystal structure of Li_xMn_3−xO₄, spinels and the nature of phase transitions. It was found that for x=0.95 the sample remains tetragonal in the whole 10–300 K temperature range. The stoichiometric LiMn₂O₄ transforms from cubic to orthorhombic at about 280 K. For x=1.0125 the temperature of phase transition from cubic to orthorhombic decreases down to about 260 K, whereas for x=1.025 the transformation goes from cubic to tetragonal phase, at the temperature 220 K. No phase transition has been observed for the cubic sample with x=1.0375. These results partly explain the divergences in recent reports on the low-temperature structure and phase transformations of lithium manganese oxides.     

Magnetic phase transition in ɛ-In x Fe2 − x O3 nanowires

This paper reports on a study of magnetic properties of ordered arrays of ?-In _x Fe_{2 ? x} O₃ (x = 0.24) nanowires possessing a high room-temperature coercive force of 6 kOe. Lowering the temperature below 190 K brings about a sharp decrease of the coercive force and magnetization of nanowires driven by the magnetic phase transition from the ferrimagnetic into antiferromagnetic phase. The transition is accompanied by a decrease of the magnetic anisotropy constant, which accounts for the anomalous frequency dependence of the position of the maximum in the temperature dependence of dynamic magnetic susceptibility. In the low-temperature phase, a spin-flop transition in the magnetic field of 28 kOe has been observed at T = 2 K. Lines related to the high-temperature hard-magnetic and low-temperature phases have been identified in electron spin resonance spectra of the nanowires. A line lying near zero magnetic field and evolving from the nonresonant signal related to the microwave magnetoresistance of the sample has also been detected.     

Charge ordering and lattice dimerization in α′-NaV2O5: One or two phase transitions?

The charge redistribution and the structural change in the α′-NaV₂O₅ quasi-one-dimensional magnet that are initiated at the transition to the low-temperature charge-ordered, structurally dimerized nonmagnetic phase was studied by optical Fourier spectroscopy. Polarized far-infrared transmission spectra obtained in the temperature region T=6–300 K were used to measure the temperature dependences of the charge-ordering-induced variation of the refractive index and of the intensity of the folded phonon mode which forms in the doubling of the lattice period. The charge-ordering and the structural phase-transition temperatures were found to coincide, T _co≈T _c ≈34 K.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.     

Resistance measurements at high pressure in the system BaPb1-xBixO3

Resistance measurements have been made in the system BaPb_1-xBi_xO₃ at pressures of up to ～ 125 kbar at room temperature. A distinct change in slope of R/R₀ vs P indicates the onset of a transition, possibly to the metallic state, which takes place continuously over a wide range of pressure.     

Neutron diffraction studies of the magnetic properties of Pr0.5Sr0.5Co1 ? x Mn x O3 solid solutions

The crystal structure and magnetic properties of a system of Pr_0.5Sr_0.5Co_{1 ? x} Mn _x O₃ solid solutions were studied by neutron diffraction and magnetization measurements. It is shown that, at a low manganese concentration, the structure can be described by the I/2a monoclinic space group; with increasing substitution level x the structure becomes orthorhombic. For x > 0.9 the crystal structure is tetragonal at high temperatures and the symmetry is lowered to orthorhombic with lowering the temperature. The substitution of cobalt for manganese leads to the destruction of long-range ferromagnetic order near x ?? 0.25. A transition from the high-temperature ferromagnetic phase to the A-type low-temperature antiferromagnetic phase is observed at x ?? 0.93 in the temperature range 110?C160 K.     

Neutron diffraction investigation of the structural transition in HgSe1−x Sx ternary mercury chalcogenide systems at high pressures

The structure of HgSe_1?x S_x ternary mercury chalcogenides at high pressures up to 35 kbar is investigated by neutron diffraction. It is found under pressure, that the HgSe_1?x S_x compounds undergo, a phase transition from the cubic sphalerite-type to the hexagonal cinnabar-type structure, which is accompanied by a jump-wise change in the unit cell volume and interatomic distances. The unit cell parameters and the positional parameters of Hg and Se (S) atoms in the high-pressure hexagonal phase are determined. A two-phase state is revealed in the phase transition region.     

Dynamical transport behavior in electron-doped manganites La0.4Ca0.6(Mn1−x Ru x )O3

Measurements of the dynamical electrical transport behavior are performed on electron-doped manganites La_0.4Ca_0.6(Mn_1−x Ru _x )O₃ (x=0 and 0.02). An undoped sample possesses a robust charge-ordered antiferromagnetic ground state, and only a positive resistivity relaxation can be observed. However, a low-temperature negative relaxation behavior arises after inducing a few ferromagnetic orders to the charge-ordered matrix by tiny Ru doping. We assigned this difference to the dynamical competition between ferromagnetic metallic and charge-ordered insulating phases. Consistently, for a doped sample, the crossover from positive to negative resistivity relaxation behavior ensues around T=115 K, which is just below the ferromagnetic Curie temperature.     

Peculiarities of the magnetic,galvanomagnetic, elastic,and magnetoelastic properties of Sm<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> manganites

Manganites of the Sm1?xSr_xMnO₃ system (x=0.33, 0.4, and 0.45) possess giant negative values of the magnetoresistance Δρ/ρ and the volume magnetostriction ω near the Curie temperature T_C. In the compound with x=0.33, the isotherms of Δρ/ρ, ω, and magnetization σ exhibit smooth variation and do not reach saturation up to maximum magnetic field strengths (120 kOe) studied (according to the neutron diffraction data, this substance comprises a ferromagnetic (FM) matrix with distributed clusters of a layered antiferromagnetic (AFM) structure of the A type). In the compounds with x=0.4 and 0.45 containing, besides the FM matrix and A-type AFM phase, a charge-ordered AFM phase of the CE type (thermally stable to higher temperatures as compared to the A-type AFM and the FM phases), the same isotherms measured at T ≥ T_C show a jumplike increase in the interval of field strengths between H_c1 and H_c2 and then reach saturation. In the interval H_c1 > H > H_c2, the σ, ω, and Δρ/ρ values exhibit a metastable behavior. At temperatures above T_C, the anisotropic magnetostriction changes sign, which is indicative of rearrangements in the crystal structure. The giant values of ω and Δρ/ρ observed at T ≥ T_C for all compounds, together with excess (relative to the linear) thermal expansion and a maximum on the ρ(T) curve, are explained by the phenomenon of electron phase separation caused by a strong s-d exchange. The giant values of magnetoresistance and volume magnetostriction (with ω reaching ～10^?3) are attributed to an increase in the volume of the FM phase induced by the applied magnetic field. In the compound with x=0.33, this increase proceeds smoothly as the FM phase grows through the FM layers in the A-type AFM phase. In the compounds with x=0.4 and 0.45, the FM phase volume increases at the expense of the charge-ordered CE-type AFM structure (in which spins of the neighboring manganese ions possess an AFM order). The jumps observed on the σ(H) curves, whereby the magnetization σ reaches ～70% of the value at T=1.5 K, are indicative of a threshold character of the charge-ordered phase transition to the FM state. Thus, the giant values of ω and Δρ/ρ are inherent in the FM state, appearing as a result of the magnetic-field-induced transition of the charge-ordered phase to the FM state, rather than being caused by melting of this phase.     

Exciton condensation in intermediate valent Sm0.90La0.10S

Sm_1−xLa_xS for x more than a few percents are metals at ambient conditions. At low temperature and high pressure they develop a small gap in the order of some meV and become semiconductors or insulators. This has been interpreted as a manifestation of the excitonic insulator. In this Letter we will concentrate on Sm_0.90La_0.10S, which is the only composition showing a first order transition. Measurements of the volume change with pressure at ambient temperature show this first order volume collapse at 5 kbar with hysteresis. The resistivity is measured in function of temperature and pressure and exhibits also at 5 kbar and ambient temperature a first order phase transition to a more metallic state. At low temperatures and in function of pressure the resistivity exhibits a peak. The optical reflectivity at 300 K has been measured at low and high pressure and transforms with pressure above 5 kbar into the golden metallic phase.     

Superconducting coherent quasiparticle weight in high-Tc superconductor from angle-resolved photoemission

We study the doping and temperature dependence of the single-particle coherent weight, z_A, for high-T_c superconductors Bi₂Sr₂CaCu₂O_8+x using angle-resolved photoemission. We find that at low temperatures the coherent weight z_A at (π,0) is proportional to the carrier concentration x and that the temperature-dependence of z_A is similar to that of the c-axis superfluid density. We show that, for a wide range of carrier concentration, the superconducting transition temperature scales with the product of the low-temperature coherent weight and the maximum superconducting gap.     

Transparent ferroelectric ceramics PbMg1/3Nb2/3O3-xPbZr0.53Ti0.47O3: Dielectric and electro-optical properties

Lanthanum-free high-transparency ferroelectric ceramics PbMg_1/3Nb_2/3O₃?xPbZr_0.53Ti_0.47O₃ (PMN-xPZT) have been prepared for the first time by a two-stage sintering method. The dielectric and electro-optical properties of the PMN-xPZT ceramics of different compositions, with the values of x both far from the morphotropic phase boundary (x = 10, 16, 23%) and close to it (x = 33%), have been studied. It has been shown that, in compositions lying closer to the morphotropic phase boundary (x = 23 and 33%), one observes, with no electric field applied, a first-order phase transition to a macrodomain ferroelectric phase, whereas the compositions far from the boundary (x = 10, 16%) persist in the relaxor cubic phase down to the low-temperature domain. It has been found that, in the ceramic with x = 33%, the quadratic electro-optical coefficients have at high temperatures (T > 340 K) the largest value among the relaxor systems, which expands the temperature interval of applicability of these solid solutions in industry.     

Phase transitions in xPbZr0.53Ti0.47O3-(1 − x)Mn0.4Zn0.6Fe2O4 magnetoelectric composites

The elastic, inelastic, and dielectric properties of the magnetoelectric composite xPbZr_0.53Ti_0.47O₃-(1 ? x)Mn_0.4Zn_0.6Fe₂O₄ (PZT-MZF) are studied in the temperature range from room temperature to 673 K. The influence of the ferroelectric PZT phase on the magnetic phase transition and the magnetic MZF phase on the ferroelectric phase transition is revealed. It is established that, as the PZT content increases, the degree of diffuseness of the phase transition decreases and a gradual crossover from a pronounced relaxor behavior to a more ordered ferroelectric behavior occurs.     

Charge-Ordered Antiferromagnetic to Ferromagnetic Phase Transition in Cr-Doped Nd0.5Ca0.5Mn1−x Cr x O3: EMR and Magnetization Study

The Cr-doped rare-earth manganites Nd_0.5Ca_0.5Mn_1−x Cr _x O₃ (x = 0.03, 0.05, 0.10) are studied by electron magnetic resonance (EMR) and magnetization measurements in the paramagnetic as well as in the ferromagnetic phase. The magnetization measurements show that the charge-ordered antiferromagnetic phase decreases at the expense of ferromagnetic metallic phase and for Cr doping of x = 0.1, the charge-ordered phase melts completely. The EMR shows multiple signals for all three compositions in the ferromagnetic phase indicative of an anisotropic ferromagnetic phase. The difference between the shift of the high-field and low-field signals decreases with Cr doping, indicating that the magnetic anisotropy decreases with the Cr doping. In the paramagnetic phase the EMR line width follows Causa's model as observed in other colossal magnetoresistant manganites. Authors' address: Ajay Sharma, Department of Physics, Indian Institute of Science, Bangalore, India     

Anomalies in the magnetic and magnetoelastic properties of Sm<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> single crystals (<Emphasis Type="Italic">x</Emphasis> ∼ 0.5) at phase transitions

By studying the magnetic and magnetoelastic properties, it is established that, as the temperature is lowered, Sm_1?xSr_xMnO₃ single crystals (x=0.5, 0.55) undergo spontaneous phase transitions from the paramagnetic to a local charge-ordered state at T_co=220 K and to an A-type antiferromagnetic state at T_N=175 K. It is shown that strong magnetic fields (H_cr ～ 200 kOe) break up the antiferromagnetic order and charge ordering and drive a phase transition to a conducting ferromagnetic state. H-T phase diagrams are constructed for single crystals with x=0.5 and 0.55.     

LARGE MAGNETIC ENTROPY CHANGE NEAR CHARGE-ORDERED TRANSITION TEMPERATURE IN PEROVSKITE-TYPE MANGANITE

The magnetocaloric effect in polycrystalline of Pr_1-xSr_xMnO₃ (x=0.33, 0.43, 0.50) has been investigated. A large magnetic entropy change (7.1J/kgK) was discovered in Pr_0.5Sr_0.5MnO₃ under a low magnetic field of 1T at charge-ordered state transition temperature (161K). The physical mechanism is related to a drastic magnetization change at a temperature where the field-induced magnetic, electron and structural phase transitions occur (from the antiferromagnetic charge-ordered state to the ferromagnetic charge-disordered state).     

Phase separation region in the phase diagram of polycrystalline Pr0.65Ca0.35−xSrxMnO3

We have performed measurements of thermoelectric power, electrical resistivity and DC magnetization in polycrystalline samples of Pr_0.65Ca_0.35−xSr_xMnO₃ with x=0, 0.02, 0.05, 0.10 and 0.20. The system presents an evolution from a charge-ordered manganite at x=0, with an insulating-like resistivity and low magnetization values, towards a ferromagnetic (FM) metallic state for x=0.20. We show that in the intermediate region a strong competition between the FM double-exchange and the localized charge-ordering occurs, inducing the phase segregation of the two competing states in a wide temperature range. We estimate the temperature (T) evolution of the FM phase fraction of the x=0.10 sample and construct a complete T−x phase diagram.     

Dual structures and transition regions in <Emphasis Type="Italic">x</Emphasis>PbTiO<Subscript>3</Subscript>-(1−<Emphasis Type="Italic">x</Emphasis>)Pb(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> crystals

Model concepts of dual structures are developed as applied to crystals of xPbTiO₃-(1?x)Pb(Zn_1/3Nb_2/3)O₃ solid solutions in the range 0 ≤ x ≤ 0.08. The conditions of the formation of dual structures upon partial and complete relaxation of internal mechanical stresses are considered. A new model of transition regions is proposed for analyzing several variants of changing the unit cell parameters that satisfy the condition of complete stress relaxation inside the transition regions in crystals at concentrations x = 0.045 and 0.08. The influence of the intermediate phase P4mm and stability of its 90° domain structure on the formation of dual structures at x ≥ 0.045 is discussed.     

Control of the temperature hysteresis and diffuse dielectric anomaly in the temperature range of the ferroelectric-antiferroelectric phase transition in PbZr1 − x TixO3 (0.03 ≤ x ≤ 0.05) ceramics

The magnitudes of the temperature hysteresis and diffuse dielectric anomaly corresponding to the transition from the antiferroelectric phase to the ferroelectric phase in PbZr_{1 ? x} Ti_xO₃ (0.03 ≤ x ≤ 0.05) ceramics can be reversibly changed by varying the temperatures of heating and cooling in the course of thermocycling. The results obtained indicate that the antiferroelectric-ferroelectric transition in the PbZr_{1 ? x} Ti_xO₃ ceramics materials is a smeared first-order phase transition.     

Specific heat anomalies in the quasi two-dimensional monophosphate tungsten bronzes KxP4W8O32

The monophosphate tungsten bronzes K_xP₄W₈O₃₂ (0.75<x<2) are quasi-two-dimensional conductors which show electronic transitions at a critical temperature T_c depending on the concentration of the alkali metal. The phase diagram shows a maximum at for x=1.30. We report specific heat measurements in the range 120-190 K. The thermal anomalies found at the transition temperature are larger than in conventional charge density wave materials. This corroborates that the transition is not a ‘pure’ charge density wave transition and that a structural transition dominates the instability.