Anomalous behavior of ultrasonic properties near 50 K in Rb0.30MoO3 and Rb0.30(Mo1−xVx)O3

Depending on the temperature, the charge density wave (CDW) nonlinear conductivity of the blue bronzes A_0.30MoO₃ (A=K, Rb) shows two different regimes: a strongly damped motion above ∼50 K and motion with almost no damping below ∼50 K. In a search for an elastic signature of this CDW behaviour, we performed ultrasonic measurements on Rb_0.30MoO₃ and Rb_0.30(Mo_1−xV_x)O₃ single crystals between 4 K and 300 K. In Rb_0.30MoO₃, at T∼50 K, upon cooling, a large increase of the sound velocity is observed. The ultrasonic attenuation coefficient shows an increase down to 50 K followed by a plateau. In Rb_0.30(Mo_1−xV_x)O₃ (x=0.4 at%) the anomaly broadens and is shifted towards higher temperatures. The results are discussed in terms of CDW glass.     

Polarized infrared reflectivity study in charge density wave conductor Tl0.3MoO3

Polarized infrared reflectivity measurements between 300 and 10 K have been carried out on charge density waves (CDW) conductor blue bronze Tl_0.3MoO₃. Three important features are observed: (i) A bump at 1155 cm⁻¹ in the reflectivity spectra of Tl_0.3MoO₃ at 300 K is a precursor of the Peierls gap due to optical excitations across a pseudogap, and this kind of Peierls-like gap opens gradually with decreasing temperature from 180 to 160 K. (ii) The three sharp modes as “triplet” of infrared reflectivity between 800 and 1000 cm⁻¹ of Tl_0.3MoO₃ along [1 0 2] axis show red shift compared to K_0.3MoO₃ and Rb_0.3MoO₃, which is assigned to the increase of the distance of Mo-O bond with the substitution of thallium ions. (iii) Two peaks at about 514 and 644 cm⁻¹ in the far-infrared reflectivity spectra of Tl_0.3MoO₃ along [1 0 2] direction are suggested to be the electronic transitions from the valence band to the midgap state and from occupied midgap state to the conduction band, respectively.     

Influence of Pr-doping on structural, electronic transport, magnetic properties of perovskite molybdates Sr1−xPrxMoO3 (0≤x≤0.15)

The effect of Pr-doping on structural, electronic transport, magnetic properties in perovskite molybdates Sr_1−xPr_xMoO₃ (0≤x≤0.15) has been investigated. The Pr-doping at Sr-site does not change the space group of the samples, but decreases the lattice parameter a. The magnitude of resistivity ρ increases initially (x≤0.08) and then decreases with further increasing Pr-doping level x and ρ(T) behaves as T² and T dependence in the low-temperature range blow T* and high-temperature range of 150 K<T<350 K, related to the electron-electron (e-e) and electron-phonon (e-ph) scattering, respectively. The magnetic susceptibility χ value of the sample increases with increasing x and the χ(T) curve for all samples can be well described by the model of exchange-enhanced paramagnetism. The specific heat magnitude in the low-temperature region increases with increasing Pr-doping level. The specific heat value agrees with the classical Dulong-Petit phonon specific heat, C_cl=3k_BrN_A=124.7 J/mol K in the high-temperature region and the temperature dependence of the specific heat can be well described by the formula C_p(T)/T=γ_e+β_pT² in the low-temperature range. These behaviors can be explained by the competition between the increase in the density of state (DOS) at Fermi energy level and the disorder effect due to Pr-doping.     

Temperature dependence of the second threshold field for rubidium blue bronze Rb0.3MoO3

We have investigated the threshold properties of Rubidium blue bronze Rb_0.3MoO₃ under high dc electric field in a large temperature range 20-150 K. The second threshold fields have been observed at temperature up to 102.4 K, and have quasi-linear relationships with temperatures 20-45 K and 55-100 K, respectively. A novel crossover platform has been found firstly in the temperature dependence of the second threshold field E_T2 at about 45-55 K. The results indicate that the dynamical behavior of the second threshold effects may originate from different mechanisms. We suggest that the highly conducting state at 20-45 K and 55-100 K result from the undamped sliding motion of rigid CDW and current inhomogeneity, respectively.     

Charge-density wave instability and nonlinear transport in Tl0.3MoO3 a new blue molybdenum oxide bronze

Single crystals of Tl_0.3MoO₃ blue bronze were grown by the temperature gradient flux technique for the first time. Tl_0.3MoO₃ crystalizes with monoclinic symmetry, space group C2, C2/m or Cm, $\text{a = 18.486(1)}\text{A}\text{?}$, $\text{b = 7.5474(6)}\text{A}\text{?}$, $\text{c = 10.0347(7)}\text{A}\text{?}$, β = 118.377(6)° and appears to be isostructural with the K_0.3MoO₃ blue bronze. The physical properties of Tl_0.3MoO₃ are similar to those of the K₃MoO₃ and Rb₃MoO₃ phases. The resistivity of Tl_0.3MoO₃ is highly anisotropic and its temperature susceptibility (4.2–300K) decreases sharply with decreasing temperature near the transition seen in the resistivity. The onset of another transition <60K is also indicated by the susceptibility data. Non-linear current-voltage (I–V) characteristics observed at ～70K above applied threshold voltages of the order of ～300mV/cm suggest the sliding of charge density condensate.     

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.     

Anomalous thermoelectric power behaviour in PrSn3 and NdSn3

Results of the thermoelectric power (TEP) measurements done on monocrystalline samples of RESn₃ compounds (RE=La, Pr, Nd, and Gd) are presented for the temperature range of 5.5-300 K. It was found that the TEP is positive and weakly temperature dependent at temperatures T>100 K. For T<100 K pronounced anomalies have been observed for the PrSn₃ and the NdSn₃ compounds in the vicinity of 10 K.We argue that the Kondo and crystal field effects cause these anomalies. A shape of the TEP anomaly found for PrSn₃ resembles very much that observed in the electrical resistivity.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Metastable states in phase separated electron doped Sm0.15Ca0.85MnO3

In order to study the mechanism behind the phase separation scenario in the Sm_0.15Ca_0.85MnO₃ compound, magnetization and resistivity measurements have been carried out in pulsed magnetic fields up to 50 T at temperatures 4.2 K<T<200 K. It is found that external magnetic field causes a collapse of a C-type AFM (P2₁/m) phase resulting in field-induced insulator-metal transition, which is irreversible below T₁=75 K. In zero field the content of a G-type phase in the mixed C-G state can vary from 10 to 17% at T=10 K. A set of metastable states with different volume ratios of G-type to C-type phases is observed below T₁ depending on the history of the sample. The obtained results indicate that the phase separation plays a dominant role for the electric and the magnetic properties of this material.     

Spin-glass-like behaviour and magnetic order in Mn[Cr0.5Ga1.5]S4 spinels

Magnetization and susceptibility were investigated as a function of temperature and magnetic field in polycrystalline Mn[Cr_0.5Ga_1.5]S₄ spinel. The dc susceptibility measurements at 919 Oe showed a disordered ferrimagnetic behaviour with a Curie-Weiss temperature θ_CW=−55 K and an effective magnetic moment of 5.96 μ_B close to the spin-only value of 6.52 μ_B for Cr³⁺ and Mn²⁺ ions in the 3d³ and 3d⁵ configurations, respectively. The magnetization measured at 100 Oe revealed the multiple magnetic transitions with a sharp maximum at the Néel temperature T_N=3.9 K, a minimum at the Yafet-Kittel temperature T_YK=5 K, a broad maximum at the freezing temperature T_f=7.9 K, and an inflection point at the Curie temperature T_C=48 K indicating a transition to paramagnetic phase. A large splitting between the zero-field-cooled (ZFC) and field-cooled (FC) magnetizations at a temperature smaller than T_C suggests the presence of spin-glass-like behaviour. This behaviour is considered in a framework of competing interactions between the antiferromagnetic ordering of the A(Mn) sublattice and the ferromagnetic ordering of the B(Cr) sublattice.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.     

Magnetic field influence on the low temperature heat capacity of the spin-Peierls compound CuGeO3

We have investigated the effect of magnetic field on the low-temperature heat capacity C_p of the undoped spin-Peierls inorganic compound CuGeO₃ in the dimerized phase. Below 1 K, C_p is dominated by a Schottky anomaly, which is removed above 1 K for field B higher than 3 T. This anomaly is well accounted for by a molar concentration x=0.75×10⁻³ of intrinsic defects, which occur predominantly on the Cu chains. This amount is confirmed by magnetization measurements. A second contribution, varying as T^−ν with ν=1 or 2, rises up with the field for B>1 T in the lower temperature range (from 70 mK to 0.3 K). At high field this contribution becomes very sensitive to the experimental dynamics.     

Positron annihilation lifetime studies on La0.5Pb0.5Mn1−yCryO3

Concentration dependent positron annihilation lifetime (PAL) measurements on Cr doped La_0.5Pb_0.5Mn_1−yCr_yO₃ (y=0.075, 0.15, 0.3, 0.35, 0.45) samples showing metal-insulator transitions (MIT) between 178 and 276 K (depending on y) reveal anomalous variation of average and bulk PAL, τ_av and τ_B, respectively, around y=0.35. Such anomaly has not, however, been observed from the corresponding magnetic susceptibility and resistivity data. Interestingly, the model parameters (polaron radius, number of ion sites per unit volume) obtained from fitting the high temperature (above MIT, T_p) resistivity data with small polaron hopping model show the signature of the said anomaly around the same concentration. Nonlinear variations of τ_av and τ_B support the existence of small polarons (T>T_p) which act as defect centers in such rare-earth manganites. Analysis of X-ray diffraction pattern confirms a change of lattice parameters indicating a structural transformation from rhombohedral (for y≤0.30) to orthorhombic (for y≥0.35) in the present system.     

Double metal-insulator peaks and effect of Sm substitution on magnetic and transport properties of hole-doped La0.85Ag0.15MnO3

La_0.85−xSm_xAg_0.15MnO₃ (x=0−0.2) ceramics were prepared using the conventional solid-state synthesis method to investigate the effect of Sm³⁺ substitution on magnetic and electrical transport properties. Magnetic susceptibility versus temperature measurements showed all samples exhibit ferromagnetic to paramagnetic transition with Curie temperature, T_c decreasing from 283 K (x=0) to 164 K (x=0.2) with increasing Sm³⁺. The observed slope in susceptibility, χ′ versus temperature curves below T_c indicates the possible presence of FM and AFM phases in the metallic region. In addition, a deviation from the Curie-Weiss law above T_c in 1/χ′ versus T curves indicates the existence of a Griffith's phase in the x=0.05−0.2 samples due to the Sm³⁺ ion substitution. The Griffith temperature, T_G was found to decrease from 295 K (x=0.05) to 229 K (x=0.2). Electrical resistivity measurements of the samples in zero field showed transition from metallic behavior to insulating behavior as the temperature was increased. For x=0, two metal-insulator, MI transition peaks were observed at T_p1=282 K and at T_p2=250 K. Both peaks shifted to lower temperatures with the increase in Sm³⁺. The relative resistivity of the first peak to the second peak decreases with increasing Sm³⁺ for x>0.05 while at x=0.2 the T_p1 peak was strongly suppressed. Magnetoresistance, MR was observed to weaken with Sm³⁺ substitution. The metallic region of the ρ(T) curve of the x=0−0.15 samples was fitted to the model of electron-electron and electron-magnon scattering while the insulating region was fitted to the variable range hopping, VRH model. The resistivity behavior indicated that the substitution of Sm³⁺ weakened the double exchange process and enhanced the Jahn-Teller effect. Our results indicated that the T_p1 peak is strongly related to the double-exchange mechanism while the T_p2 peak is suggested to originate from magnetic inhomogeneity.     

Spin glass like behavior in Cd0.42Mn0.58In2S4

The magnetic behavior of the diluted magnetic semiconductor Cd_0.42Mn_0.58In₂S₄ has been study by dc magnetization and ac susceptibility experiments. Zero field cooled and field cooled measurements reveal irreversibility below T_irr=2.60±0.15 K. Ac susceptibility data, performed as a function of the temperature and the frequency, confirm the spin-glass like behavior of the material with T_f=2.75±0.15 K. High temperature susceptibility data follow a typical Curie-Weiss law with θ=−74±1 K which suggests predominant antiferromagnetic interactions. The randomness of the magnetic ions, necessary to explain the magnetic behavior of the material, has been determined by X-ray powder diffraction experiments.     

Electrical properties of KTiOPO4 single crystal in the temperature range from −100 °C to 100 °C

The electrical property of a KTiOPO₄ single crystal was studied by means of a dielectric spectroscopy method in the temperature range from −100 to 100 °C. Dielectric dispersion began at a temperature, T_S=−80 °C. It is believed that this dielectric dispersion is related to the ionic hopping conduction, which arises mainly from the jumping of K⁺ ions. The activation energy concerned with hopping conduction is E_a∼0.20 eV above T_S. T_S=−80 °C can be the minimum temperature for the hopping K⁺ ion.     

K0.3MoO3和Tl0.3MoO3派尔斯相变临界行为的比热研究

采用连续绝热加热法测量了K_0.3MoO₃和Tl_0.3MoO₃在100—220K温度范围内的比热。发现K_0.3MoO₃和Tl_0.3MoO₃分别在177.5K和172.3K发生派尔斯相变。对派尔斯相变附近比热临界行为的研究表明,K_0.3MoO₃和Tl_0.3MoO₃的临界区域宽度分别为6K和8K,临界行为属于三维XY模型普适类。 关键词：     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

Magnetic properties of the novel nanocomposite (Zn0.15Ni0.85Fe2O4)0.15/(SiO2)0.85 at room temperature

The value of the effective magnetic anisotropy constant of the ferrimagnetic nanoparticles Zn_0.15Ni_0.85Fe₂O₄ embedded in a SiO₂ silica matrix, determined through ferromagnetic resonance (FMR), is much higher than the magnetocrystalline anisotropy constant. The higher value of the anisotropy constant is due to the existence of surface anisotropy. However, even if the magnetic anisotropy is high, the ferrimagnetic nanoparticles with a 15% concentration, which are isolated in a SiO₂ matrix, display a superparamagnetic (SPM) behavior at room temperature and at a frequency of the magnetization field equal to 50 Hz. The FMR spectrum of the novel nanocomposite (Zn_0.15Ni_0.85Fe₂O₄)_0.15/(SiO₂)_0.85, recorded at room temperature and a frequency of 9.060 GHz, is observed at a resonance field (B_0r) of 0.2285 T, which is substantially lower than the field corresponding to free electron resonance (ESR) (0.3236 T). Apart from the line corresponding to the resonance of the nanoparticle system, the spectrum also contains an additional weaker line, identified for a resonance field of ∼0.12 T, which is appreciably lower than B_0r. This line was attributed to magnetic ions complex that is in a disordered structure in the layer that has an average thickness of 1.4 nm, this layer being situated on the surface of the Zn_0.15Ni_0.85Fe₂O₄ nanoparticles that have a mean magnetic diameter of 8.9 nm.