Li2Mo2O6多晶材料的结构与电性能的研究

本文用固相反应烧结制备出Li₂Mo₂O₆多晶材料。经X射线分析、红外光谱和电子顺磁共振谱(EPR)的研究,确定了它的结构是Li₂Mo₂O₄和MoO₂两个晶相组成的烧结体。钼离子以四价状态存在于MoO₂晶相结构中。采用交流阻抗谱分析了晶界与温度变化的相关性。测得了样品的ln(σ_总T)-1/T 曲线是由两段直线和一段曲线所组成;总电导率化能σ_27℃=1.36×10^-3(Ω·cm)^-1,σ_115℃=1.49×10^-3(Ω·cm)^-1,σ_300℃=9.71×10^-3(Ω·cm)^-1,σ_370℃=2.42×10^-3(Ω·cm)^-1;电导活化能E₁=0.043eV,E₂=0.235eV,E_平均=0.76eV。采用维格纳极化电池法测得电子电导率σ_e,σ_e27℃=2.240×10^-5(Ω·cm)^-1,σ_e300℃=4.476×10^-3(Ω·cm)^-1。实验证明,室温下材料为固体电解质,300℃附近为良好的离子与电子混合导体。 关键词：     

Luminescence and energy transfer in TbAl3B4O12

An investigation of the luminescence properties of TbAl₃B₄O₁₂ in the temperature region 1.4–300 K is reported. Laser site-selection and time-resolution techniques were used.The results show that energy migration among Tb³⁺ ions on the regular crystallographic sites occurs. The transfer characteristics at room temperature are consistent with a diffusion-limited transfer process to Mo³⁺ quenching centres. The diffusion constant and the critical transfer distance for Tb³⁺ → Mo³⁺ transfer are derived. The rate of diffusion increases for decreasing temperature. At about 60 K a transition from diffusion-limited transfer to trapping-limited transfer occurs. This behaviour is due to the variation in the diffusion constant with temperature. In the temperature region below 60 K transfer to Tb³⁺ traps is observed. The intensity of the emission from the traps increases exponentially with decreasing temperature. However, the overall transfer rate to Mo³⁺ and traps remains roughly constant. A simple model including time-independent transfer rates and back transfer from traps to intrinsic Tb³⁺ ions is proposed to explain the results. The rates of transfer to Mo³⁺ and traps are obtained.     

Thermoelectric properties of sol-gel derived cobaltite Bi2Ca2.4Co2Oy

Layered misfit cobaltite Bi₂Ca_2.4Co₂O_y has been synthesized by a sol-gel method. This compound exhibits large thermoelectric (TE) power (S_300 K∼170 μV K⁻¹), low resistivity (ρ_300 K∼42 mΩ cm) and relatively small thermal conductivity (κ_300 K∼2.8 W K⁻¹ m⁻¹) at room temperature. Furthermore, the resistivity of this compound displays a metallic behavior above T^?∼150 K with a semiconducting behavior below this temperature. This abnormal behavior in resistivity is analogous to those observed in Sr and Ba based misfit cobaltites. The observed features of the TE have been discussed based on the narrow band model.     

The phase transition, hygroscopicity, and thermal expansion properties of Yb2-xAlxMo3O12

Materials with the formula Yb2-xAlxMo3O12 （x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1.0, 1.1, 1.3, 1.5, and 1.8） were synthesized and their structures, phase transitions, and hygroscopicity investigated using X-ray powder diffraction, Raman spectroscopy, and thermal analysis. It is shown that Yb2-xAlxMo3012 solid solutions crystallize in a single monoclinic phase for 1.7 〈 x 〈 2.0 and in a single orthorhombic phase for 0.0 〈 x 〈 0,4, and exhibit the characteristics of both monoclinic and orthorhombic structures outside these compositional ranges. The monoclinic to orthorhonlbic phase transition temperature of A12Mo3012 can be reduced by partial substitution of A13＋ by Yb3＋, and the Yb2-zAlxMo3012 （0.0 〈 x 〈 2.0） materials are hydrated at room temperature and contain two kinds of water species. One of these interacts strongly with and hinders the motions of the polyhedra, while the other does not. The partial substitution of A13＋ for Yb3＋ in Yb2Mo3012 decreases its hygroscopicity, and the linear thermal expansion coefficients after complete removal of water species are measured to be -9.1 x 10-6/K, -5.5 x 10-6/K, 5.74 x 10-6/K, and 9.5 x 10 6/K for Ybl.sAlo.2（MoO4）3, Yb1.6Alo.4（MoO4）3, Ybo.4All.6（Mo04）3, and Ybo.2Al1.8（MoO4）3, respectively.     

Modified texture and high temperature transport properties of doubly substituted BaxAgyCa2.8Co4O9 thermoelectric oxide

Doubly substituted polycrystalline compound bulk samples of Ba_xAg_yCa_2.8Co₄O₉ were prepared via citrate acid sol-gel method followed by spark plasma sintering. The phase composition, orientation, texture and high temperature electrical properties were systematically investigated. The results showed that the orientation and the texture could be modified by altering ratio of Ba to Ag. The resistivity and the Seebeck coefficient of substituted samples were decreased by decreasing Ba/Ag ratio except for that of Ba_0.1Ag_0.1Ca_2.8Co₄O₉ sample with lowest electrical resistivity (7.2 mΩ cm at 973 K), moderately high Seebeck coefficient (172 μV/K at 973 K) and improved power factor (0.42 mW/mK² at 973 K).     

Electrical properties of thin films of Eu2O3 substituted compounds

Europium oxide (Eu₂O₃) substituted compound has been prepared by solid-solid reaction of the powders of Eu₂O₃, BaCO₃ and CuO at 950°C for 16 hours. The thin films have been deposited by high vacuum evaporation technique (vacuum ≈ 10⁻⁶ torr). The variation of current (I) with voltage (V) at room temperature (RT) i.e. 294 K and in ice (273 K) are found to be linear. The variation of electrical resistivity (ρ) with temperature (T) by heating the sample above RT has been determined. Resistivity is found to decrease with increase in temperature. Further the variation of electrical resistivity (ρ) with temperature (T) from 77 K, liquid nitrogen temperature (LNT), to 270 K has also been determined. It is observed that resistivity suddenly becomes zero at around 87 K. Thus the prepared material has superconducting properties with superconducting transition temperature, T _c at 87 K.      

Spray pyrolytic deposition of solid electrolyte Bi2V0.9Cu0.1O5.35 films

Copper substituted bismuth vanadate films have been successfully deposited first time by spray pyrolysis technique on glass substrates suitable for low temperature solid oxide fuel cells. Desired phase formation of polycrystalline Bi₂V_0.9Cu_0.1O_5.35 (BICUVOX.10) was confirmed by X-ray diffraction technique. These films were further studied with EDAX and SEM techniques for their compositional and morphological characterization. Electrical conductivity of BICUVOX.10 is found to be 5.7 × 10⁻² (Ω cm)⁻¹ at 698 K, predicts the onset temperature for ionic contribution suitable for low temperature SOFC applications. Room temperature complex impedance plot reveals that electrical process arises due to contribution from the grain interior.     

Structural and electrical behavior of Pb(Mg1/4Cd1/4Mo1/2)O3 ceramics

Preliminary X-ray structural analysis of polycrystalline Pb(Mg_1/4Cd_1/4Mo_1/2)O₃ ceramics, prepared by a solid-state reaction technique, provides single-phase orthorhombic structure at room temperature. Detailed dielectric studies of the material as a function of temperature reveal a sharp phase transition at temperature T_c=49°C obeying Curie-Weiss behavior. Scanning electron microscope (SEM) studies of the sample show the uniform distribution of grains in the samples. A dielectric anomaly and ferroelectric phase transition observed at 49°C was supported by polarization studies. The activation energy of the sample was calculated from the dielectric data. The variation of dc resistivity with temperature suggests that the compound behaves as a negative temperature coefficient resistor (NTCR).     

Spray pyrolytic synthesis of samarium doped ceria (Ce0.8Sm0.2O1.9) films for solid oxide fuel cell applications

Uniform, adherent, single phase samarium doped ceria films have been successfully deposited by spray pyrolysis technique for their application in solid oxide fuel cell. These films have been deposited at different substrate temperatures on glass substrate and subsequently heat treated in tube furnace. Effect of substrate temperature and annealing temperature on phase formation was studied with thermo-gravimetric analysis and differential temperature analysis, X-ray diffraction, scanning electron microscope, and energy dispersive X-ray analysis techniques. These studies showed the formation of single phase Ce_0.8Sm_0.2O_1.9 films, at substrate temperature 400 °C and annealing temperature 550 °C. Electrical resistivity of the films, at room temperature was of the order of 10⁷ Ω cm while at 400 °C it is found to be of the order of 10¹ Ω cm. This reveals the use of these films for making low temperature solid oxide fuel cells.     

Li2Mo2-xWxO6多晶材料的结构、电学性能与导电机理的研究

本文采用还原气氛制备导电性能优良的多晶多相陶瓷材料Li₂Mo_2-xW_xO₆(x=0,0.1,0.3),采用粉末X射线衍射分析、特征X射线能谱分析、红外光谱分析和电子自旋共振波谱分析等现代测试手段,得到样品的物相结构为Li₂Mo_1-xW_xO₄和MoO₂两相组成。W的掺入主要取代Mo进入Li₂ 关键词：     

EPR observation of a high temperature phase transition in Zn(ClO4)2·6H2O:Mn2+

The electron paramagnetic resonance of Mn²⁺ doped in single crystals of Zn(ClO₄)₂·6H₂O has been studied at X-band in the temperature range 300–380 K. A phase transition, observed at ～ 346 K, is reported for the first time.     

Substrate temperature influenced structural, electrical and optical properties of dc magnetron sputtered MoO3 films

Molybdenum oxide (MoO₃) films were deposited on glass and (1 1 1) silicon substrates by sputtering of metallic molybdenum target in an oxygen partial pressure of 2 × 10⁻⁴ mbar and different substrate temperatures in the range 303-623 K using dc magnetron sputtering technique. X-ray photoelectron spectrum of the films formed at 303 K showed asymmetric Mo 3d_5/2 and Mo 3d_3/2 peaks due to the presence of mixed oxidation states of Mo⁵⁺ and Mo⁶⁺ while those deposited at substrate temperatures ≥473 K were in Mo⁶⁺ oxidation state of MoO₃. The films formed at substrate temperatures ≥473 K were polycrystalline in nature with orthorhombic α-phase MoO₃. Fourier transform infrared spectra of the films showed an absorption band at 1000 cm⁻¹ correspond to the stretching vibration of MoO, the characteristic of the α-MoO₃ phase. The electrical resistivity increased from 3.3 × 10³ to 8.3 × 10⁴ Ω cm with the increase of substrate temperature from 303 to 473 K respectively due to improvement in the crystallinity of the films. Optical band gap of the films increased from 3.03 to 3.22 eV with the increase of substrate temperature from 303 to 523 K.     

射频反应性溅射沉积的Cd2SnO4薄膜物理性质与缺陷特性研究

在Ar+O₂混合气氛中射频反应性溅射Cd-Sn合金靶制备了透明导电Cd₂SnO₄(简称CTO)薄膜。用X射线衍射测量了CTO膜的结构。实验结果表明,这种薄膜的电学和光学性质依赖于混合气体中的氧浓度、衬底温度以及沉积后的热处理。获得的CTO膜最低电阻率为1.74×10^-6Ω·cm,可见光光谱区最高透射率为95％。对于氧浓度为6％、衬底温度为400℃时沉积的CTO膜,经热处理后,其光隙能由热处理前的2.37eV增大为2.6 关键词：     

High temperature thermoelectric properties of highly c-axis oriented Bi2Sr2Co2Oy thin films fabricated by pulsed laser deposition

High-temperature thermoelectric transport property measurements have been performed on the highly c-axis oriented Bi2Sr2Co20v thin films prepared by pulsed laser deposition on LaA1Oa （001）. Both the electric resistivity p and the seebeck coefficient S of the film exhibit an increasing trend with the temperature from 300 K-1000 K and reach up to 4.8 m. cm and 202 V/K at 980 K, resulting in a power factor of 0.85 mW/mK which are comparable to those of the single crystalline samples. A small polaron hopping conduction can be responsible for the conduction mechanism of the film at high temperature. The results demonstrate that the Bi2Sr2Co2Oy thin film has potential application has high temperature thin film thermoelectric devices,     

Structure and low-temperature properties of Ba8Ni6Ge40

Structural, magnetic, heat capacity, electrical and thermal transport properties are reported on polycrystalline Ba₈Ni₆Ge₄₀. Ba₈Ni₆Ge₄₀ crystallizes in a cubic type I clathrate structure with unit cell a=10.5179 (4) Å. It is diamagnetic with susceptibility χ_dia=−1.71×10^-6 emu/g Oe. An Einstein temperature 75 K and a Debye temperature 307 K are estimated from heat capacity data. It exhibits n-type conducting behavior below 300 K. It shows high Seebeck coefficients (−111×10^-6 V/K), low thermal conductivity (2.25 W/K m), and low electrical resistivity (8.8 mΩ cm) at 300 K.     

Curie temperature,crystallization temperature and electrical resistivity as a function of composition for Fe80-xMoxB20 metallic glasses

The influence of the substitution of small amounts of Fe with Mo (0–10 at.%) in a Fe₈₀B₂₀ metallic glass on the Curie temperature, crystallization temperature and room temperature electrical resistivity is reported. A decrease in Curie temperature of approximately 40 K/at.% Mo is observed. The crystallization temperatures show a small increase with increasing Mo-content, and the room temperature electrical resistivity of the as quenched samples is essentially independent of the Mo-content (?^am(295 K) ～ 128 μχ-cm).     

Magnetic and electrical transport properties in the self-doped manganite La0.9Mn0.9M0.1O3 (M=Mn,Zn and Ti)

The magnetic and electrical transport properties of La_0.9Mn_0.9M_0.1O₃ (M=Mn, Zn and Ti) were investigated. The temperature and magnetic field dependence of electrical resistivity (ρ) and dc magnetization were studied. All the compounds are found in rhombohedral structure. The excess oxygen in all three compounds was detected through iodometric titration. A modification in resistivity is observed when M=Mn is replaced by M=Zn and Ti. The high temperature resistivity above T_C follow variable range hopping model for both Zn and Ti compounds. For Zn doping, the observation of large field-cool effect and decrease in resistivity at room temperature and is assumed to be due to the implant of Mn⁴⁺ in Mn³⁺ matrix, which favor Mn³⁺/Mn⁴⁺ double exchange. The ferromagnetic behavior below T_C for the compound with M=Ti is correlated to the excess oxygen in it, which implants Mn⁴⁺ and thus incorporates ferromagnetic interactions. The substitutions lead to a reduction of T_c and magnetization.     

Physical properties of several M2Mo6X6 compounds (M = GROUP IA METAL; X = Se,Te)

We report the physical properties of the pseudo one dimensional ternary molybdenum chalcogenides M₂Mo₆X₆ (M = K, Rb,Cs,Tl;X = Se, Te) measured on single crystals grown at high temperature. For Group IA metals (Rb,..,Cs) the transport properties evolve from a metallic to a semiconducting-like behavior on decreasing the temperature. Over the same temperature range the Group IIIA compound (Tl₂Mo₆Se₆) remains metallic and even superconducts at 5.1K. The susceptibility of these materials is weakly diamagnetic and does not reveal anomalied correlated to the onset of the broad metal-nonmetal transition, except perhaps for Cs₂Mo₆Te₆. A variation of the electronic interchain coupling is proposed to explain the difference between the Group IA and IIIA metal compounds. In the absence of evidence of three dimensional ordering at low temperature, we suggest that the broad metal-nonmetal transition is due to a fluctuating Pierls gap that is uncorrelated from one Mo chain to the next.     

Low temperature magnetoresistance in La1.32Sr1.68Mn2O7 layered manganite under hydrostatic pressure

The La_1.32Sr_1.68Mn₂O₇ layered manganite system has been studied by the low temperature electrical resistance and magnetoresistance under hydrostatic pressure up to 25 kbar. We have observe both, a Curie temperature (T_C) and a metal-insulator transition (T_MI) at 118 K in the ambient pressure. The applied pressure shifts the T_MI to higher temperature values and induces a second metal-insulator transition (T²_MI) at 90 K, in the temperature dependence of resistivity measurements. Also, the pressure suppresses the peak resistance abruptly at T_C. When an external field of 5 T is applied, we have observed a large negative magnetoresistance of 300% at the transition temperature and a 128% at 4.5 K. However, the increased pressure decreases the magnetoresistance ratio gradually. When the pressure reaches its maximum available value of 25 kbar, the magnetoresistance ratio decreases at a rate of 1.3%/kbar. From our experimental results, the decrease of magnetoresistance ratio with pressure is explained by the pressure induced canted spin state which is not favor for the spin polarized intergrain tunneling in layered manganites.     

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.