The pressure influence on the incommensurate-commensurate ferroelectric phase transition in [4-NH2C5H4NH][SbCl4]

The dielectric properties of the [4-NH₂C₅H₄NH] SbCl₄ (abbreviated as 4-APCA) crystal were investigated under hydrostatic pressure up to 300 Mpa. The pressure-temperature phase diagram was given. The paraelectric-ferroelectric phase transition (II→III) temperature (T_c) increases linearly with increasing pressure with a slope dT_c/dp=21×10⁻² K/MPa. The pressure dependence of Curie-Weiss constants has been evaluated also. In the paraelectric phase (II) the Curie constant (C₊) was pressure dependent whereas the C₋ constant over the ferroelectric phase (III) was almost constant. The results are interpreted in terms of improper and displacive type phase transition model with a soft phonon at a zone boundary.     

The effect of hydrostatic pressure on the ferroelectric phase transition in [NH2(CH3)2]3[Sb2Cl9]

The effect of hydrostatic pressure on the ferroelectric phase transition temperature in [NH₂(CH₃)₂]₃[Sb₂Cl₉] (DMACA) has been studied by electric permittivity measurements at pressures up to 400 MPa. The pressure-temperature phase diagram is given. The phase transition temperature (T_c) increases with increasing pressure up to 150 MPa, passes through a maximum and then decreases with a further increase of pressure. The unexpected nonlinear decrease in T_c with pressure increasing above 150 MPa suggests that the mechanism of ferroelectric phase transition in DMACA is different from hitherto assumed.     

Crystallographic study of the phase transition in (Me4P)2ZnBr4

The compound (Me₄P)₂ZnBr₄, a member of the β-K₂SO₄ structure class, undergoes a phase transition at 84°C from the room temperature space group P12₁/c1 to the parent Pmcn structure. The room temperature structure corresponds to a ferrodistortive transition of B_1g symmetry at the zone center. At room temperature, the compound has lattice constants a=9.501(1), b=16.055(2), c=13.127(2) Å and β=90.43(1)°. For the high temperature phase, the orthorhombic cell has dimensions a=9.466(2), b=16.351(3) and c=13.284(2) Å. The structures consist of two crystallographically independent Me₄P⁺ cations and the ZnBr₄²⁻ anions. In the room temperature phase, all three ionic species show substantial displacement from the mirror plane perpendicular to the a-axis that exists in the high temperature phase, as well as rotations out of that plane. The thermal parameters of the cations are indicative of substantial librational motion. Measurements of lattice parameters have been made at 2-5°C intervals over the temperature range 40-140°C. The changes in the lattice constants appear continuous at T_c (within experimental limits) indicating that the phase transition is likely second-order. The a lattice constant shows an anomalous shortening as T_c is approached. Thermal expansion coefficients are calculated from this data. An application of Landau theory is used to derive the temperature dependencies of spontaneous shear strain and corresponding elastic stiffness constants associated with the primary order parameter.     

Structure of the low-temperature phase of Rb3D(SeO4)2 by single-crystal neutron diffraction

Crystal structure of Rb₃D(SeO₄)₂ has been investigated at 25 K (below the transition temperature T_c=95.4 K) by single-crystal neutron diffraction. Accompanying the transition, the SeO₄ groups, which are all equivalent in the phase above the transition (space group A2/a), split into eight nonequivalent groups in a superlattice (a×2b×2c, space group A2) in the low-temperature phase. Based on the D atom positions obtained, each of the SeO₄ groups was identified to be in the state closer to a HSeO₄⁻ ion or to a SeO₄²⁻ ion and the dipole arrangement of SeO₄-D-SeO₄ dimer was revealed. This dipole arrangement has ‘ferri’ structure along the polar b-axis, but ‘antiferro’ structure in the plane perpendicular to the b-axis. These results are consistent with the characteristics found in the earlier dielectric measurements.     

The roles of “ammonium” and “hydrogen-bond” protons in single crystals of the superionic conductor NH4HSeO4 by H NMR relaxation

The variations with temperature of the line-shape, spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, of the ¹H nuclei in NH₄HSeO₄ single crystals were investigated, and with these ¹H NMR results we were able to distinguish the crystals’ “ammonium” and “hydrogen-bond” protons. The line width of the signal due to the ammonium protons abruptly narrows near the temperature of the superionic phase transition, T_SI, which indicates that they play an important role in this phase transition. The ¹H T₁ for NH₄⁺ and HSeO₄⁻ in NH₄HSeO₄ do not change significantly near the ferroelectric phase transition of T_C1 (=250 K) and the incommensurate phase transition of T_i (=261 K), whereas they change near the temperature of the superionic phase transition T_SI (=400 K). Our results indicate that the main contribution to the low-temperature phase transition below T_SI is that of the molecular motion of ammonium and hydrogen-bond protons, and the main contribution to the conductivity at high temperatures above T_SI is the breaking of the O-H?O bonds and the formation of new H- bonds in HSeO₄⁻. In addition, we compare these results with those for the NH₄HSO₄ and (NH₄)₃H(SO₄)₂ single crystals, which have similar hydrogen-bonded structure.     

Dielectric properties and phase transitions of (Pb0.87La0.02Ba0.1)(Zr0.6Sn0.4−xTix)O3 ceramics with compositions near AFE/RFE phase boundary

The electrical properties and phase transition behavior of (Pb_0.87La_0.02Ba_0.1)(Zr_0.6Sn_0.4−xTi_x)O₃ solid solutions (PLBZST, 0.04≤x0.2) were investigated by the X-ray diffraction, permittivity, pyroelectric current, and P-E electric hysterisis loops. As the composition x increased from 0.04 to 0.2, the antiferroelectric ceramics (x≤0.07, AFE) with tetragonal phase changed to the ferroelectric relaxors (RFE, 0.09≤x). AFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to −100 °C) due to a frustration between AFE and FE state. With an increase in composition x, electrically field-induced AFE-FE switching field (E_AFE-FE) and AFE-paraelectric (PE) phase transition temperature (T_c) are depressed in the temperature (T)-Ti composition (x) phase diagram, a FE-AFE-PE triple phase point (T_tr) with the lowest transition temperature occurred at x=0.09. The pyroelectric currents under an application of various external electric field (E) were measured to identify a T-E phase diagram of the PLBZST compound.     

Piezoelectric measurements on BiFeO3 single crystal by Raman scattering

The piezoelectric response of BiFeO₃ at low temperature has been investigated by Raman scattering measurements. The application of an external electric field at T=10 K induces frequency shifts of the lowest frequency mode related to the Bi-O bonds and corresponding to the soft mode of the ferroelectric transition. The piezoelectric effect is responsible for the softening of this mode via the tensile stress leading to the expansion of the crystal. The phonon deformation potential associated with the soft mode has been estimated around −200 cm⁻¹/strain units using the linear piezoelectric coefficient d₃₃=16 pm/V. It found in the range of the ones obtained for typical piezoelectrics.     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

High pressure behaviour of KHSO4 studied by electrical impedance spectroscopy

Measurements of the electrical conductivity were performed in KHSO₄ at pressures between 0.5 and 2.5 GPa and in the temperature range 120-350 °C by the use of the impedance spectroscopy. The temperatures of the α-β phase transition (T_Tr) and of the melting (T_m), determined from the Arrhenius plots ln(σT) vs. 1/T, increase with pressure up to 1.5 GPa having dT/dP∼+45 K/GPa. Above the pressure 1.5 GPa, the pressure dependencies of T_Tr and T_m are negative dT/dP∼−45 K/GPa. At pressures above 0.5 GPa, the reversible decomposition of KHSO₄ into K₃H(SO₄)₂+H₂SO₄ (and probably into K₅H₃(SO₄)₄+H₂SO₄) affects the electrical conductivity of KHSO₄, with the typical values of the protonic electrical conductivity, c. 10⁻¹ S/cm at 2.5 GPa.     

Superconductivity and calorimetric studies of Pr1.85Ce0.15CuO4+δ under different annealing conditions

Polycrystalline samples of electron-doped Pr_1.85Ce_0.15CuO_4+δ have been prepared under different annealing conditions and investigated by means of X-ray-diffraction, oxygen content analysis, electrical resistivity, magnetic susceptibility and low temperature specific heat measurements. X-ray-diffraction patterns show that samples contain a single T′ phase. The superconducting transition temperatures T_cm taken with the onset of diamagnetism in magnetic-susceptibility measurements are 20 and 19.5 K for sample annealed in flowing Ar gas and in vacuum (∼10⁻³ torr), respectively. The data of the samples, which are annealed in flowing Ar gas, show clear evidence for an αT² term at zero magnetic field in superconducting electronic specific heat, and are consistent with d-wave superconductivity. However, this behavior is not observed in the other sample, which is annealed in vacuum. These results indicate that different heat treatments affect the oxygen content, homogeneity, superconducting transition temperature T_c, superconducting volume fraction, and the superconducting pairing symmetry of Pr_1.85Ce_0.15CuO_4+δ.     

X-ray diffraction, Cs and H NMR and thermal studies of CdZrCs1.5(H3O)0.5(C2O4)4·xH2O displaying Cs and water dynamic behavior

A novel mixed cadmium zirconium cesium oxalate with an open architecture has been synthesized from precipitation methods at room pressure. It crystallizes with an hexagonal symmetry, space group P3₁12 (no. 151), a=9.105(5) Å, c=23.656(5) Å, V=1698(1) Å³ and Z=3. The structure displays a [CdZr(C₂O₄)₄]²⁻ helicoidal framework built from CdO₈ and ZrO₈ square-based antiprisms connected through bichelating oxalates, which generates channels along different directions. Cesium cations, hydronium ions and water molecules are located inside the voids of the anionic framework. They exhibit a dynamic disorder which has been further investigated by ¹H and ¹³³Cs solid-state NMR. Moreover a phase transition depending both upon ambient temperature and water vapor pressure was evidenced for the title compound. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. The final product is a mixture of cadmium oxide, zirconium oxide and cesium carbonate.     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Temperature-dependent Fe Mössbauer spectroscopy and local structure of the mullite-type Bi2(FexGa1−x)4O9 (0.1≤x≤1) solid solution

The Bi₂(Fe_xGa_1−x)₄O₉ oxide solid solution possessing a mullite-type structure has been investigated by ⁵⁷Fe Mössbauer spectroscopy in dependence of composition (0.1≤x≤1) and temperature (293≤T/K≤1073). The spectra have been fitted with two doublets for tetrahedrally and octahedrally coordinated high-spin Fe³⁺ ions, respectively. The experimental areas of the subspectra were used to determine the distribution of iron on the two inequivalent structural sites. The fraction of iron cations occupying the octahedral site is found to increase with decreasing Fe content and the cation distribution is almost independent of temperature. The unusual temperature dependence of the quadrupolar splitting, QS, observed for the octahedral site with dQS/dT>0 is discussed in connexion with structural data for Bi₂Fe₄O₉. The temperature dependence of Mössbauer isomer shifts and signal intensities is examined in the context of local vibrational properties of iron on the two inequivalent sites of the mullite-type lattice structure.     

Effect of pressure and magnetic field on bilayer La1.25Sr1.75Mn2O7 single crystal

We report the temperature dependence of susceptibility for various pressures, magnetic fields and constant magnetic field of 5 T with various pressures on La_2−2xSr_1+2xMn₂O₇ single crystal to understand the effectiveness of pressure and magnetic field in altering the magnetic properties. We find that the Curie temperature, T_c, increases under pressure (dT_c/dP=10.9 K/GPa) and it indicates the enhancement of ferromagnetic phase under pressure up to 2 GPa. The magnetic field dependence of T_c is about 26 K for 3 T. The combined effect of pressure and constant magnetic field (5 T) shows dT_c/dP=11.3 K/GPa and the peak structure is suppressed and broadened. The application of magnetic field of 5 T realizes 3D spin ordered state below T_c at atmospheric pressure. Both peak structure in χ_c and 3D spin ordered state are suppressed, and changes to 2D-like spin ordered state by increase of pressure. These results reveal that the pressure and the magnetic field are more competitive in altering the magnetic properties of bilayer manganite La_1.25Sr_1.75Mn₂O₇ single crystal.     

Li- and V-NMR study of LiVS2

⁷Li- and ⁵¹V-NMR have been measured to make clear the electronic state in a two-dimensional triangular lattice LiVS₂. Knight shift of both ⁷Li- and ⁵¹V-NMR is almost independent of temperature below the phase transition temperature T_c of about 310 K from the paramagnetic state to non-magnetic state. The ⁵¹V- spin-lattice relaxation rate 1/T₁ reveals an exponential temperature dependence below T_c, indicating a gap structure of electronic state. These results are consistent with a non-magnetic state with a trimer singlet of V³⁺ spins below T_c.     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

A novel high-k ‘Y5V’ barium titanate ceramics co-doped with lanthanum and cerium

Structural, dielectric, and ferroelectric properties of a novel high-k ‘Y5V’ (Ba_1−xLa_x)(Ti_1−x/4−yCe_y)O₃ ceramics (where x=0.03 and y=0.05, denoted by BL3TC5) with the highest ‘Y5V’ dielectric response (ε′>10 000) among rare-earth-doped BaTiO₃ ceramics to date are investigated in detail using SEM, TEM, XRD, DSC, EPR, Raman spectroscopy (RS), temperature and frequency, electric field dependences of dielectric permittivity (ε′), and temperature and electric field dependences of ferroelectric hysteresis loops. The BL3TC5 diffusion of ferroelectric phase transition occurs around dielectric peak temperatures (T_m) near a room temperature characteristic of dielectric thermal relaxation. Powder XRD data and defect complex model were given. “Relaxor” behavior associated with an order/disorder model and formation of a solid solution were discussed. The EPR results provided the evidence of Ti vacancies as compensating for lattice defects. High-k relaxor nature of BL3TC5 is characterized by an average cubic structure with long-range lattice disordering and local polar ordering; a slow change of the ε′ (T) and P_r(T) curves around T_m; no phase transition observed by DSC; and a broad, red-shifted A₁ (TO₂) Raman phonon mode at 251 cm⁻¹ accompanying the disappearance of the “silent” mode at 305 cm⁻¹ and a clear anti-resonance effect at 126 cm⁻¹ at room temperature.     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Study of the magnetization and transport properties of the La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 (0≤x≤0.2) system

The samples with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 La_(2+x)/3Sr_(1−x)/3Mn_1−xCr_xO₃ (0≤x≤0.20) have been prepared. The magnetic, electrical transport, and magnetoresistance properties have been investigated. Remarkable transport and colossal magnetoresistance (CMR) effect, as well as cluster glass (CG) behaviors have been clearly observed in the samples studied. It was found that the Curie temperature T_c and insulator−metal transition temperature T_p1 are strongly affected by Cr substitution. The experiment observations are discussed by taking into account the variety of tolerance factors t; the effects of A-site radius 〈r_A〉 and the A-site mismatch effect (σ²).     

Suppression of Tc by Zn impurity in the electron-type LaFe0.925−y Co0.075ZnyAsO system

The effect of non-magnetic Zn impurity on superconductivity in electron-type pnictide superconductor LaFe_0.925−yCo_0.075Zn_yAsO is studied systematically. The optimally doped LaFe_0.925Co_0.075AsO without Zn impurity exhibits superconductivity at T_c^mid of 13.2 K, where T_c^mid is defiend as the mid-point in the resistive transition. In the presence of Zn impurity, the superconducting transition temperature, T_c^mid, is severely suppressed. The result is consistent with the theoretic prediction on the effect of non-magnetic impurity in the scenario of s_± pairing, but it is in sharp contrast to the previous report on the effect of Zn impurity in the F-doped systems. The possible interpretation of the different effects of Zn impurity on superconductivity in different systems is discussed.