Superconductivity at 5.5 K in Nb<Subscript>2</Subscript>PdSe<Subscript>5</Subscript> Compound

We report superconductivity in as-synthesized Nb₂PdSe₅, which is similar to a recently discovered Nb₂PdS₅ compound having very high upper critical field, clearly above the Pauli paramagnetic limit Zhang et al. (Sci. Rep. 3:1446, 2013). A bulk polycrystalline Nb₂PdSe₅ sample is synthesized by a solid-state reaction route in a phase-pure structure. The structural characterization has been done by X-ray diffraction, followed by Rietveld refinements, which revealed that the Nb₂PdSe₅ sample is crystallized in a monoclinic structure within the space group C2/m. Structural analysis revealed the formation of sharing of one-dimensional PdSe₂ chains. Electrical and magnetic measurements confirmed the superconductivity in Nb₂PdSe₅ compound at 5.5 K. Detailed magneto-resistance results exhibited the value of upper critical field to be around 8.2 T. The estimated H _c2(0) is within the Pauli paramagnetic limit, which is unlike the Nb₂PdS₅.     

Reactions of V<Subscript>2</Subscript>O<Subscript>5</Subscript>, Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>, and Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> with AlN

Reactions of vanadium, niobium, and tantalum pentoxides with aluminum nitride have been studied using X-ray diffraction. At temperatures from 1000 to 1600°C, we have identified various V, Nb, and Ta nitrides. The composition of the niobium and tantalum nitrides depends on the reaction temperature. The tendency toward nitride formation becomes stronger in the order V₂O₅ < Ta₂O₅ < Nb₂O₅.     

Superconductivity at 4.4 K in PdTe<Subscript>2</Subscript> Chains of a Ta-Based Compound

Superconductivity in PdTe₂ heavy transition metal-based compounds is a rapidly developing field in condensed matter physics community. Here, we report superconductivity in a nominal ternary telluride Ta₂Pd_0.97Te₆ compound, which is synthesized in sealed evacuated quartz ampoule. The resultant compound is crystallized in layered monoclinic Ta₄Pd₃Te₁₆ phase with space group C2/m, having lattice parameters a = 21.304(6)Å, b = 3.7365(7)Å and c = 17.7330Å with β = 120.65(1)^°. Both transport and magnetic measurements demonstrated bulk superconductivity at 4.4 K in studied polycrystalline sample. The metallic normal state conductivity can be well ascribed to Fermi liquid behaviour. The superconducting upper critical field of the compound is determined to be 5.5 T based on magnetoresistivity measurements.     

Synthesis and Superconductivity of Layered Compounds with Orthogonal [Zr<Subscript>2</Subscript>N<Subscript>2</Subscript>] Network

Layered α-form ZrNX (X: Cl and Br) compounds with high quality were prepared by chemical vapor transport. The intercalation of alkali metal A (A: Li, Na, K, Rb) was carried out to realize electron doping into the orthogonal [Zr₂N₂] layers. The Rietveld refinement analysis reveals that the [Zr₂N₂] crystalline layers in the intercalation compounds shift mutually in the ab plane when compared with the hosts. Magnetic measurements show that the intercalation compounds A _x ZrNX are changed into superconductors with transition temperature T _c of up to 12 K. Upon the cointercalation of solvent molecules such as THF, T _c decreases to as low as 6.1 K with increasing the interlayer spacing d up to 14 Å, which is similar to the d dependence of T _c recently found in electron-doped α-form TiNX series. We also succeeded in synthesizing another new polymorph of α-Zr₂N₂S by the topochemical reaction between α-form ZrNX and Na₂S. α-Zr₂N₂S (space group: Immm, a = 4.1375(1) Å, b = 3.5422(1) Å, and c = 11.5204(3) Å) has the same α-[Zr₂N₂] layers, whereas the interlayer spacing between two adjacent [Zr₂N₂] layers is effectively decreased by 1/3 when compared with the parent compounds of ZrNX.     

Anharmonicity in the V<Subscript>2</Subscript>O<Subscript>3</Subscript> molecule and thermodynamic properties of V<Subscript>2</Subscript>O<Subscript>3</Subscript> in the gas phase

A quantum-mechanical calculation of the relative stability, structural parameters, and vibrational frequencies of V₂O₃ molecule isomers for different spin states was carried out using the BPW91/6-311+G(d, p) method. It was shown that the isomer with the C _s structure (nonplanar VOVO rectangle with an O atom attached to it) in the X ⁵ A″ electronic state possesses the maximum stability. The energy of the C _2v symmetry structure was higher than the lowest energy by just 23 cm⁻¹. It definitely indicated the impossibility of usage of the harmonic model in order to calculate the thermodynamic functions of V2O3 (g). A model is proposed based on which the energy levels and vibrational sums of states for this type of motion were calculated for the C _s → C _2v → C _s transition coordinate. These data, as well as results obtained from quantum-mechanical calculations, were used to calculate the thermodynamic functions of V₂O₃ (g) in the temperature range of T = 100–6000 K. The calculations were performed with the five excited electronic states with energies from 1000 to 9000 cm⁻¹ taken into account. A comparison with the data calculated in the “rigid rotator-harmonic oscillator” approximation was performed.     

Superconductivity in Ca<Subscript>0.5</Subscript>La<Subscript>0.5</Subscript>FBiSe<Subscript>2</Subscript>

Through the measurement of resistivity, magnetic susceptibility, and Hall effect, we discovered a novel BiSe₂-based superconductor Ca_0.5La_0.5FBiSe₂ with T _c of 3.9 K. A strong diamagnetic signal below T _c in susceptibility χ(T) is observed indicating the bulk superconductivity. The negative Hall coefficient throughout the whole temperature regime implies the dominant electron-type carriers in the sample. Different to most of BiS₂-based compounds where superconductivity develops from a semiconducting-like normal state, its resistivity in the present compound exhibits a metallic behavior down to T _c . Together with the enhanced T _c , the metallic character of the normal state implies that the electronic structure of Ca_0.5La_0.5FBiSe₂ may be different to those in the other BiS₂-based compounds.     

Ginzburg-Landau Analysis on the Superconductivity in TlNi<Subscript>2</Subscript>Se<Subscript>2</Subscript>

Based on a two-band isotropic Ginzburg-Landau theory, we study the magnetic properties of the recently observed superconducting crystal TlNi₂Se₂. Our exact solution of upper critical field reproduces the experimental data in a broad temperature range. It directly underlies the multi-gap superconductivity in this crystal. We also show that the effective mass of the electron for one band is about 20m _e while that of the other band is only 0.6m _e. This semi-heavy-fermion feature can qualitatively explain the experimental value of the Kadowaki-Woods ratio in TlNi₂Se₂.     

Polycrystalline materials in MoO<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript>–V<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Melt quenching technique was applied to study tendency for phase formation and amorphization in the MoO₃–ZrO₂–V₂O₅ system. By X-ray diffraction were detected the main crystalline phases separated during the quenching: Zr(MoO₄)₂, V₂MoO₈, (Mo_0.3V_0.7)₂O₅, V_0.95Mo_0.97O₅ but in a wide concentration range the dominant crystalline phase was monoclinic ZrO₂. The average particle sizes of the obtained crystal phases were in the range 30–50 nm. A narrow glass formation area was situated, near MoO₃–V₂O₅ side. The glass-crystalline samples were obtained in the MoO₃- and V₂O₅-rich compositions. The phase formation was proven by IR analysis also. IR data showed that the main structural units built up the glass network are corner shared VO₅ and MoO₆ groups while in the corresponding crystal V₂MoO₈ phase MeO₆ (Me = V, Mo) octahedra are corner and edge shared (band at 580 cm⁻¹).     

Enhancement in electrical conductivity of Li<Subscript>2</Subscript>O: B<Subscript>2</Subscript>O<Subscript>3</Subscript>: V<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

The study of electrical conductivity of 30Li₂O: (70 − x) B₂O₃: xV₂O₅ glass samples has been carried out. The results have been explained by dividing the temperature range into two regions. In region I, conductivity shows Arrhenius behaviour for all the samples. The conductivity increases with addition of V₂O₅. The results have been explained in the light of Anderson and Stuart Model. In region II, an anomalous enhancement in the conductivity is observed for all the samples up to certain temperature beyond which the conductivity decreases. The enhancement in the conductivity in the annealed glass sample has been attributed to nanocrystallization.     

Thermoanalytical study of the polymorphism and melting behavior of Cu<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>

We have developed a procedure for the synthesis of phase-pure α- and β-Cu₂V₂O₇. Thermal analysis and X-ray diffraction demonstrate that the β-phase (monoclinic structure) exists at low temperatures (stability range 25–610°C), while α-Cu₂V₂O₇ (orthorhombic structure) is stable in the range 610–704°C. The α-phase observed during cooling, in particular at room temperature, is in a metastable state. The melting of the high-temperature phase γ-Cu₂V₂O₇, which forms between 704 and 716°C, has the highest rate in the range 770–785°S and is accompanied by peritectic decomposition and oxygen gas release. Subsequent cooling gives rise to four exothermic peaks, one of which (780.9°C) is attributable to the crystallization of the peritectic melt, one (620.1°C) is due to the γ → α → β phase transformations of Cu₂V₂O₇, and the other two arise from the crystallization of multicomponent low-melting-point eutectics containing α- and β-Cu₂V₂O₇, CuVO₃, and other compounds.     

Impedance spectroscopy of Ba<Subscript>3</Subscript>Sr<Subscript>2</Subscript>DyTi<Subscript>3</Subscript>V<Subscript>7</Subscript>O<Subscript>30</Subscript> ceramic

Polycrystalline sample of Ba₃Sr₂DyTi₃V₇O₃₀ was prepared at 950°C using a high-temperature solid-state reaction technique. X-ray structural analysis indicated the formation of a single-phase orthorhombic structure with lattice parameters: a = 12·2719 (39) Å, b = 8·9715(39) Å and c = 19·7812(39) Å. Microstructural study showed densely packed uniform distribution of grains over the surface of the sample. The a.c. impedance plots were used as tools to analyse the electrical response of the sample as a function of frequency at different temperatures (30–500°C). These plots revealed the presence of grain boundary effect, from 200·C onwards. Complex impedance analysis showed non-Debye type of dielectric relaxation. The Nyquist plots showed the negative temperature coefficient of resistance character of Ba₃Sr₂DyTi₃V₇O₃₀. A hopping mechanism of electrical transport processes in the system is evident from the modulus analysis. The activation energy of the compound (calculated both from loss and modulus spectrum) is the same, and hence the relaxation process may be attributed to the same type of charge carrier.     

Electrical properties of V<Subscript>2</Subscript>O<Subscript>5</Subscript>-CaO-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses exhibiting majority charge carrier reversal

The thermoelectric power and d.c electrical conductivity of x V₂O₅⋅40CaO⋅(60−x)P₂O₅ (10 ≤ x ≤ 30) glasses were measured. The Seebeck coefficient (Q) varied from +88 μ V K⁻¹ to −93 μV K⁻¹ as a function of V₂O₅ mol%. Glasses with 10 and 15 mol% V₂O₅ exhibited p-type conduction and glasses with 25 and 30 mol% V₂O₅ exhibited n-type conduction. The majority charge carrier reversal occurred at x = 20 mol% V₂O₅. The variation of Q was interpreted in terms of the variation in vanadium ion ratio (V^{5 +}/V^{4 +}). d.c electrical conduction in x V₂O₅⋅40CaO⋅(60−x)P₂O₅ (10 ≤ x ≤ 30) glasses was studied in the temperature range of 150 to 480 K. All the glass compositions exhibited a cross over from small polaron hopping (SPH) to variable range hopping (VRH) conduction mechanism. Mott parameter analysis of the low temperature data gave values for the density of states at Fermi level N (E_F) between 1.7 × 10²⁶ and 3.9 × 10²⁶ m⁻³ eV⁻¹ at 230 K and hopping distance for VRH (R_VRH) between 3.8 × 10⁻⁹m to 3.4 × 10⁻⁹ m. The disorder energy was found to vary between 0.02 and 0.03 eV. N (E_F) and R_VRH exhibit an interesting composition dependence.     

Interplay of Superconductivity and Ferromagnetism in UGe<Subscript>2</Subscript>

The emergence of pressure induced superconductivity (SC) under the background of ferromagnetic state in 5f-electron based itinerant ferromagnetic superconductor UGe₂ is studied in the single band model by using a mean-field approximation. The solutions to the coupled equations of superconducting gap (Δ) and magnetization (m) are obtained using Green’s function technique and equation of motion method. It is shown that there generally exists a coexistent (Δ≠0, m≠0) solution to the coupled equations of the order parameters in the temperature range 0<T<min (T _C,T _FM), where T _C and T _FM are respectively the superconducting and ferromagnetic transition temperatures. The study of electronic specific heat (C/T), density of states, free energy, etc. are also presented. The specific heat capacity at low temperature shows linear temperature dependence as opposed to the activated behavior. Density of states increases as opposed to the case of a standard ferromagnetic metal. Free energy study reveals that the superconducting ferromagnetic state has lower energy than the normal ferromagnetic state and, therefore, realized at low enough temperature. The agreement between theory and experimental results for UGe₂ is quite satisfactory.      

Electrical Conductivity and Electrochemical Characteristics of Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-Based NASICON-Type Materials

NASICON-type materials with the compositions Na₃V_2–xAl_x(PO₄)₃, Na₃V_{2 - x}Fe_x(PO₄)₃, Na_{3 + x}V_2–xNi_x(PO₄)₃, and Na₃V_{2 - x}Cr_x(PO₄)₃ (x = 0, 0.03, 0.05, and 0.1) have been prepared and characterized by X-ray diffraction analysis, electron microscopy, and impedance spectroscopy. The results demonstrate that the highest electrical conductivity among the samples studied is offered by the material doped with 5% Fe: Na₃V_1.9Fe_0.1(PO₄)₃. The activation energy for low-temperature conduction in the doped materials decreases from 84 ± 2 to 54 ± 1 kJ/mol and that for high-temperature conduction is ~33 kJ/mol. The discharge capacity of Na₃V_1.9Fe_0.1(PO₄)₃/C under typical working conditions of cathodes of sodium ion batteries has been shown to exceed that of Na₃V₂(PO₄)₃/C. The capacity of the more porous material prepared by the Pechini process (Na₃V_1.9Fe_0.1(PO₄)₃/C-{II}) approaches the theoretical one at a low charge–discharge rate and retains its high level as the charge rate is raised (its discharge capacity was 117.6, 108.8, and 82.6 mAh/g at a discharge rate of 0.1C, 2C, and 8C, respectively).     

Structural,Magnetic, and Optoelectronic Properties of TbNi<Subscript>5</Subscript>, TbNi<Subscript>3</Subscript>Ti<Subscript>2</Subscript> and TbNi<Subscript>3</Subscript>V<Subscript>2</Subscript> Compounds

The spin-polarized, electronic, magnetic, and optical properties of TbNi₅, TbNi₃Ti₂, and TbNi₃V₂ intermetallic compounds have been calculated by employing the full-potential linear augmented plane waves (FP-LAPW) within the density functional theory (DFT) and implemented in the WIEN2k package. In this approach, the generalized gradient approximation with Hubbard U-correction (GGA + U) was chosen as exchange-correlation potential. The electronic structure such as band structure and density of states have been investigated and compared among them. The frequency dependences of dielectric function, optical absorption, reflectivity, and optical conductivity are determined. The optical spectra are changed due to the substitution of nickel with titanium and vanadium. Total and local magnetic moments of Tb, Ni, Ti, and V are also estimated; it is shown that the total magnetic moment of the three alloys is vigorously contributed by the local magnetic moment of terbium.     

Phase evolution in V<Subscript>2</Subscript>O<Subscript>5</Subscript>-H<Subscript>3</Subscript>PO<Subscript>4</Subscript>-organic component systems during barothermal treatment

Data are presented on phase changes in mixtures of vanadium pentoxide and phosphoric acid during autoclaving in organic solvents in the presence of organic reductants.     

Study of magnetic properties of two samples from FeVO<Subscript>4</Subscript>-Co<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> system

Two samples containing phases formed in the FeVO₄-Co₃V₂O₈ system were prepared by a conventional sintering method. The sample designated as H5 was one-phase with the howardevansite-type structure, while the sample designated as HL7 contained a mixture of H-type and lyonsite-type structures. The temperature dependence of the electron paramagnetic resonance (EPR) spectra and static magnetic susceptibility χ was investigated in the temperature range from liquid helium to room temperature. Both the EPR spectra and the dc magnetic susceptibility showed anomalous behavior indicating that the magnetic competition process may be responsible. A comparison of the obtained results with previous studies on related compounds with the same structure, i.e. M₃Fe₄V₆O₂₄ (M = Mg(II), Zn(II), and Cu(II)) revealed that the observed anomaly shifted to lower temperatures on replacing the non-magnetic ions by magnetic Co(II) ions. The temperature dependence of the inverse susceptibility χ ^?1 indicates the existence of antiferromagnetic interactions between Fe(III) and Co(II) spins in sample H5. The obtained values of the Curie-Weiss temperatures are lower than for the Mn₃Fe₄V₆O₂₄ compound and comparable to compounds from M₃Fe₄V₆O₂₄ systems with M diamagnetic cations. The introduction of cobalt cations intensifies the magnetic frustration what is reflected in the temperature dependence of the magnetic susceptibility at low temperatures.     

Enhanced electrochemical performance of Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>F<Subscript>3</Subscript> for Na-ion batteries with nanostructure and carbon coating

Carbon-coating Na₃V₂(PO₄)₂F₃ nanoparticles (NVPF@C NP) were prepared by a hydrothermal assisted sol–gel method and applied as cathode materials for Na-ion batteries. The as-prepared nanocomposites were composed of Na₃V₂(PO₄)₂F₃ nanoparticles with a typical size of ~?100 nm and an amorphous carbon layer with the thickness of ~?5 nm. Cyclic voltammetry, rate and cycling, and electrochemical impedance spectroscopy tests were used to discuss the effect of carbon coating and nanostructure. Results display that the as-prepared NVPF@C NP demonstrates a higher rate capability and better long cycling performance compared with bare Na₃V₂(PO₄)₂F₃ bulk (72 mA h g^?1 at 10 C vs 39 mA h g^?1 at 10 and 1 C capacity retention of 95% vs 88% after 50 cycles). The remarking electrode performance was attributed to the combination of nanostructure and carbon coating, which can provide short Na-ion diffusion distance and rapid electron migration.     

Effect of V<Subscript>2</Subscript>O<Subscript>5</Subscript> content on the optical,structural and electrochromic properties of TiO<Subscript>2</Subscript> and ZrO<Subscript>2</Subscript> thin films

Vanadium oxide (V₂O₅) mixed titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films were fabricated on glass substrates (corning 2947) and on indium tin oxide (ITO) coated glass substrates by sol gel spin coating process. Their optical, structural and electrochromic properties were investigated. The results were compared with pure TiO₂ and ZrO₂ thin films. Mixture of V₂O₅ with both types of film reduces the transmittance at the higher wavelengths. The refractive index of the V₂O₅ mixed TiO₂ and ZrO₂ films increases when compared with pure TiO₂ and ZrO₂ films. AFM images demonstrate no significant topographical changes for V₂O₅ mixed TiO₂ whereas for V₂O₅ mixed ZrO₂ films a topographical change is observed. V₂O₅ mixed TiO₂ showed slight increase in their charge capacity.