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：     

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.     

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.     

The thermoelectric power of charge-density-wave conductors Rb0.3MoO3 and Rb0.15K0.15MoO3

The thermoelectric power (TEP) of the quasi-one-dimensional charge-density-wave (CDW) conductors rubidium blue bronze Rb_0.3MoO₃ and its alloy Rb_0.15K_0.15MoO₃ were measured in the temperature range 80-280 K. The result showed a sign change from a small positive value to a great negative value where the Peierls transition temperatures (T_p) are 183 and 180 K for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃, respectively. Above T_p, the TEP for both samples can be described with the empirical relation S=AT+B; while below T_p, the TEP fits well the relation S=AT+B/T based on the experimental data. The Fermi energies ε_F for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃ are estimated to be 1.55 and 0.53 eV, respectively.     

Heat capacity of EuMnO3 and Eu0.7A0.3MnO3 (A=Ca,Sr) compounds

We carried out the heat capacity calculation of the magnetoresistance compounds EuMnO₃ and Eu_0.7A_0.3MnO₃ (where A=Ca and Sr) as a function of temperature from 5 to 100 K, using the Rigid Ion Model (RIM). The results on heat capacity for EuMnO₃ and Eu_0.7A_0.3MnO₃ (A=Ca and Sr) obtained by us are in good agreement with the measured values. Although strong electron–phonon interactions are present in these compounds but the lattice part of the specific heat also deserves proper attention. The parent compound EuMnO₃ exhibits two magnetic transitions at 35 and 47 K due to weak ferromagnetic (FM) component and antiferromagnetic (AF) ordering. In addition, we have reported cohesive energy (φ), molecular force constant (f), compressibility (β), Restrahalen frequency (υ₀), Debye temperature (θ_D) and Gruneisen parameter (γ) in the temperature range 5 K?T?100 K.     

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.     

Low temperature specific heat of bi-layered manganites La2−2xSr1+2xMn2O7 (x=0.3 and 0.5)

The specific heat (C) of bi-layered manganites La_2−2xSr_1+2xMn₂O₇ (x=0.3 and 0.5) is investigated for the ground state of low temperature excitations. A T^3/2 dependent term in the low temperature specific heat (LTSH) is identified at zero magnetic field and suppressed by magnetic fields for x=0.3 sample, which is consistent with a ferromagnetic metallic ground state. For x=0.5 sample, a T² term is observed and is consistent with a two-dimensional (2D) antiferromagnetic insulator. However, it is almost independent of magnetic field within the range of measured temperature (0.6-10 K) and magnetic field (6 T).     

Studies on fabrication of Ag/Tl2Ba2Ca2Cu3O10/CdSe heterostructures with electrochemical technique

The Ag/Tl₂Ba₂Ca₂Cu₃O₁₀/CdSe heterostructure was fabricated at room temperature by soft electrochemical processing technique for the first time. The formation of the heterostructure with non-diffusive interfaces was confirmed by X-ray diffraction. The crystallite sizes determined for Tl-2223 and CdSe films were 33 nm and 25 nm, respectively. The Tl₂Ba₂Ca₂Cu₃O₁₀ film electrodeposited onto Ag-substrate has shown the superconducting transition temperature T_c at 116.5 K and J_c = 2.1 × 10³ A/cm². These values were found to improve after the deposition of CdSe onto Ag/Tl-2223 films. The effect of red He-Ne laser irradiation on the superconducting properties of heterostructure are studied and discussed at length in this paper.     

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.     

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.     

Magnetic properties of large-area one-dimensional WO2 and MoO2 nanorods

Large-area one-dimensional (1D) monoclinic WO₂ and MoO₂ nanorods in the space group P2₁/c were synthesized by reactive thermal evaporation. The as-synthesized 1D WO₂ and MoO₂ nanorods become soft magnetic materials at 10 K, implying that structural or magnetic transitions occur. There are large differences in saturation magnetization, the coercive field, and remanence between the 1D WO₂ and MoO₂ nanorods, although both 1D nanorods have a similar shape.     

蓝青铜K0.3MoO3单晶Peierls相变研究

测量了蓝青铜K_0.3MoO₃单晶Ｒ-Ｔ曲线，发现曲线在２８０Ｋ左右有异常变化，计算得到１８０Ｋ以下的半导体能隙为１３２０Ｋ（０.１１ｅＶ）．液氮温度下测量了晶体的非线性导电性，得到电场阈值为０.1２９Ｖ／ｃｍ．样品ＤＳＣ研究表明，样品在２４０Ｋ处经历一新的Ｐｅｉｅｒｌｓ相变，且为一级相变，据此对相变的微观性质进行了定量计算．１８０Ｋ附近Δｃ_p-Ｔ曲线表明，１８０Ｋ处的相变为一个二级相变加一个一级相变 关键词：     

Possible anisotropy gap in La1.35Sr1.65Mn2O7 and La1.5Sr0.5NiO4 detected through specific heat and magnetization measurements

Magnetization and specific heat measurements, as a function of temperature, were performed on single crystals of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄, under different applied magnetic fields (H). The specific heat in La_1.35Sr_1.65Mn₂O₇ was decreased for H=9 T parallel to the crystal c axis, compared with H=0, possibly due to a suppression of spin-wave excitations (magnons) in that ferromagnetic bilayer structure. On the other hand, the applied magnetic field had no effect in the specific heat of the antiferromagnetic La_1.5Sr_0.5NiO₄. For H=9 T and below the temperature of 4 K the specific heat data, for each crystal, was well fitted by an exponential decay law. This allowed the calculation of energy gaps around 1 meV for both compounds, in close agreement with Δ=2μ_BH for an expected energy gap in the magnon spectrum. Detailed magnetization measurements showed monotonic variations below 4 K and a steep increase close to 2 K. Both magnetization and specific heat measurements suggest the existence of an anisotropy gap in the energy spectrum of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄.     

RHEED and Auger study of the MoO3(010) surface interaction with H2S/H2 mixture and pure H2S

Pure single crystals of MoO₃ were carefully grown by physical vapor transport. The initial stages of the interaction of H₂S with a MoO₃ (010) surface were studied by RHEED and AES at low pressure p <133 Pa and at T < 700 K. Three main stages were found: (a) The formation of either a completely disordered sulphur adiayer (with pure H₂S) or a superstructure MoO₃(010)-[2 × 1]S (with H₂S/H₂). (b) A reduction of MoO₃ producing oriented three-dimensional MoO₂ islands, (c) An epitaxial overgrowth of MoS₂ from the MoO₂ three-dimensional crystallites.     

Magnetic and transport properties of Pr2Pd3Si5

We have investigated the magnetic and transport properties of a new ternary intermetallic compound Pr₂Pd₃Si₅ which forms in U₂Co₃Si₅-type orthorhombic structure (space group Ibam). At low field (0.01 T) magnetic susceptibility exhibits an abrupt increase below 7 K and peaks at 5 K, revealing a magnetic phase transition. The onset of magnetic order is also confirmed by well defined anomalies in the specific heat and electrical resistivity data. Apart from the sharp λ-type anomaly, magnetic part of specific heat also shows a broad Schottky-type hump due to crystal field effect. Magnetoresistance data as a function of temperature exhibits a pronounced peak in paramagnetic state which could be interpreted in terms of crystal field effect and short-range ferromagnetic correlations.     

Valence fluctuation in Ce2Co3Ge5 and crystal field effect in Pr2Co3Ge5

Polycrystalline samples of ternary rare-earth germanides R₂Co₃Ge₅ (R=La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U₂Co₃Si₅ structure (space group Ibam). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce₂Co₃Ge₅ deviates from the expected lanthanide contraction, indicating non trivalent state of Ce ions in this compound. The reduced value of effective moment (μ_eff≈0.95 μ_B) compared to that expected for trivalent Ce ions further supports valence-fluctuating nature of Ce in Ce₂Co₃Ge₅. The observed temperature dependence of magnetic susceptibility is consistent with the ionic interconfiguration fluctuation (ICF) model. Although no sharp anomaly due to a phase transition is seen, a broad Schottky-type anomaly is observed in the magnetic part of specific heat of Pr₂Co₃Ge₅. An analysis of C_mag data suggests a singlet ground state in Pr₂Co₃Ge₅ separated from the singlet first excited state by 22 K and a doublet second excited state at 73 K.     

Analysis of low temperature specific heat in Nd0.5Sr0.5MnO3 and R0.5Ca0.5MnO3 (R=Nd,Sm, Dy and Ho) compounds

We report on the specific heat C(T) of doped manganites Nd_0.5Sr_0.5MnO₃, Nd_0.5Ca_0.5MnO₃, Sm_0.5Ca_0.5MnO₃, Dy_0.5Ca_0.5MnO₃ and Ho_0.5Ca_0.5MnO₃ in the temperature range 2?T?300 K using modified rigid ion model (MRIM). The present specific heat results are in general satisfactory agreement with experimental data except at very low temperatures (i.e. T?12 K). Also a sharp peak observed in the experimental results for these compounds around 5 K could not be revealed by our computed results as they arise due to Schottky-like anomaly. Besides, we have reported the cohesive and the thermal properties of these compounds. The results obtained by us are discussed in detail.     

Specific heat and magnetic susceptibility of single-crystalline ZnCr2−xAlxSe4 (x=0.15, 0.23)

A correlation between the second critical field H_c2 of the helix to paramagnetic transition and the magnetic specific heat C-peak was found in ZnCr_2−xAl_xSe₄ spinel single crystals with x=0.15, 0.23. The specific heat peak is anomalously sharp for all finite magnetic fields used here and this points to a first order magneto-structural transition (from cubic to tetragonal symmetry). The C(T)-peak is increasingly suppressed as the external field increases. Approaching the Neel temperature T_N, a broad ac-magnetic susceptibility peak is observed for zero dc-magnetic field. That peak does not show an energy loss and thus points towards a return to a second order type of transition. The magnetic contribution to the specific heat displays a sharp peak at T_N and is maximal at the spin fluctuation temperature T_sf=34 K. T_sf is related to the maximum of the magnetic susceptibility at T_m=40 K (at 50 kOe) in the spin fluctuation region, as evidenced by the entropy exceeding 90% of the entropy calculated classically for the complete alignment of the Cr spins, (2−x)R ln(2S+1). The X-ray photoelectron spectroscopy (XPS) data indicate that Al-substitution does not affect Cr³⁺ 3d³ electronic configuration.     

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.