Improved electrochemical performance of Li<Subscript>1.2</Subscript>Ni<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>O<Subscript>2</Subscript> cathode material with fast ionic conductor Li<Subscript>3</Subscript>VO<Subscript>4</Subscript> coating

Layered lithium-enriched nickel manganese oxides Li_1.2Ni_0.2Mn_0.6O₂ have been synthesized and coated by fast ionic conductor Li₃VO₄ with varying amounts (1, 3, and 5 wt%) in this paper. The effect of Li₃VO₄ on the physical and electrochemical properties of Li_1.2Ni_0.2Mn_0.6O₂ has been discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), discharge, cyclic performance, rate capability, and electrochemical impedance spectroscopy (EIS). The discharge capacity and coulomb efficiency of Li_1.2Ni_0.2Mn_0.6O₂ in the first cycle have been improved after Li₃VO₄ coating. And, the 3 wt% Li₃VO₄-coated Li_1.2Ni_0.2Mn_0.6O₂ shows the best discharge capacity (246.8 mAh g^?1), capacity retention (97.3 % for 50 cycles), and rate capability (90.4 mAh g^?1 at 10 C). Electrochemical impedance spectroscopy (EIS) results show that the R _ct of Li_1.2Ni_0.2Mn_0.6O₂ electrode decreases after Li₃VO₄ coating, which is due to high lithium ion diffusion coefficient of Li₃VO₄, is responsible for superior rate capability.     

Synthesis and structural,magnetic, and resonance properties of the LiCuFe<Subscript>2</Subscript>(VO<Subscript>4</Subscript>)<Subscript>3</Subscript> compound

Complex studies have been performed for the structural, static magnetic, and resonance properties of a new magnet LiCuFe₂(VO₄)₃ prepared by solid-phase synthesis. The temperature dependence of the susceptibility has an anomaly at temperature T_max = 9.6 K. At high temperatures, the LiCuFe₂(VO₄)₃ sample is in the paramagnetic state described by the Curie–Weiss law at T > 50 K and mainly determined by iron ions with effective magnetic moment μ_eff(exp) = 8.6μ_B per formula unit. At low temperatures, a long-range magnetic order is observed in the magnetic subsystem of the sample; the order is predominantly characterized by the antiferromagnetic exchange interaction and high frustration level. The exchange interaction parameters are estimated in a six-sublattice representation of the LiCuFe₂(VO₄)₃ magnet. It is shown that the LiCuFe₂(VO₄)₃ compound is an antiferromagnet with strong intrachain and frustrating interchain exchange interactions.     

Effect of oxygen partial pressure and VO<Subscript>2</Subscript> content on hexagonal WO<Subscript>3</Subscript> thin films synthesized by pulsed laser deposition technique

We report on the effect of oxygen partial pressure and vacuum annealing on structural and optical properties of pulsed laser-deposited nanocrystalline WO₃ thin films. XRD results show the hexagonal phase of deposited WO₃ thin films. The crystallite size was observed to increase with increase in oxygen partial pressure. Vacuum annealing changed the transparent as-deposited WO₃ thin film to deep shade of blue color which increases the optical absorption of the film. The origin of this blue color could be due to the presence of oxygen vacancies associated with tungsten ions in lower oxidation states. In addition, the effects of VO₂ content on structural, electrochemical, and optical properties of (WO₃)_1−x (VO₂) _x nanocomposite thin films have also been systematically investigated. Cyclic voltammogram exhibits a modification with the appearance of an extra cathodic peak for VO₂–WO₃ thin film electrode with higher VO₂ content (x ≥ 0.2). Increase of VO₂ content in (WO₃)_1−x (VO₂) _x films leads to red shift in optical band gap.     

Growth and spectral properties of self-frequency doubling crystal,Nd:Ca<Subscript>9.03</Subscript>Na<Subscript>1.08</Subscript>La<Subscript>0.62</Subscript>(VO<Subscript>4</Subscript>)<Subscript>7</Subscript>

The non-doped and doped Nd³⁺ of Ca_9.03Na_1.08La_0.62(VO₄)₇ crystals were grown by the Czochralski technique. The effective segregation coefficients of Na⁺ and Nd³⁺ ions in the crystal were measured to be about 0.5 and 1.1, respectively. The XPS analysis of Ca_9.03Na_1.08La_0.62(VO₄)₇ crystal indicates that the vanadium in the crystal is a mixture of V⁴⁺ (1.46 at. %) and V⁵⁺ (98.54 at. %). The hardness of Nd:Ca_9.03Na_1.08La_0.62(VO₄)₇ crystal is about 383.1 VDH. Nd:Ca_9.03Na_1.08La_0.62(VO₄)₇ crystal exhibits similar thermal expansion coefficients along the a (11.2×10^-6 K^-1) and c (13.7×10^-6 K^-1) axes, indicating a low thermal expansion anisotropy (α_c/α_a≈1.2). The qualitative frequency-doubling experiment shows that the doping of Na⁺ ion can help reduce the scattering of frequency-doubling light, and the intensity of SHG for Ca_9.03Na_1.08La_0.62(VO₄)₇ crystal is found to be about 3.5 times as large as that of KDP. The polarized absorption and fluorescence spectra are analyzed based on Judd–Ofelt theory, which exhibits that the π-polarized absorption and stimulated emission cross sections are 6.07×10^-20 cm² with an FWHM 12.0 nm at 810 nm and 1.42×10^-19 cm² at 1069 nm, respectively. The fluorescence lifetime is 115 μs at room temperature. All the results indicate that Nd:Ca_9.03Na_1.08La_0.62(VO₄)₇ crystal is a candidate of self-frequency doubling laser material. PACS 42.62.Fi; 42.70.Mp; 81.10.Fq     

Ordered monoclinic vanadium suboxide V<Subscript>14</Subscript>O<Subscript>6</Subscript>

The monoclinic (space group C2/m) superstructure of the suboxide V₁₄O₆, which is formed as a result of the atomic and vacancy ordering of the tetragonal solid solution of oxygen in vanadium, is investigated using X-ray diffraction and symmetry analysis. The monoclinic suboxide V₁₄O₆ is observed in the vanadium oxide samples VO_0.57, VO_0.81, and VO_0.86 synthesized at 1770 K and the samples VO _y (0.87 ≤ y ≤ 0.98) additionally annealed at 1470 K after the synthesis. It is established that the channel of the disorder-order phase transition associated with the formation of the monoclinic suboxide V₁₄O₆ includes six superstructure vectors belonging to three non-Lifshitz stars of one type {k ₁}. The distribution function of the oxygen atoms in the monoclinic superstructure of the suboxide V₁₄O₆ is calculated. It is demonstrated that the displacements of vanadium atoms distort the body-centered tetragonal metal sublattice, thus preparing the formation of the facecentered cubic sublattice and the transition from the suboxide V₁₄O₆ to the cubic vanadium monoxide with the B1 structure.     

Experimental study on doubly QML Nd:Lu<Subscript>0.15</Subscript>Y<Subscript>0.85</Subscript>VO<Subscript>4</Subscript> laser with AO modulator and central SESAM

By using double-mixed crystal Nd:Lu_0.15Y_0.85VO₄ as laser medium, a diode-pumped doubly Q-switched and mode-locked (QML) Nd:Lu_0.15Y_0.85VO₄ laser with acousto-optic (AO) modulator and central semiconductor saturable absorption mirror (SESAM) is realized for the first time. The Q-switched envelope modulation depth is nearly 100%.The average output power and the pulse width of the Q-switched envelope etc. for different AO modulator repetition rates have been measured. The experimental result show that Nd:Lu_0.15Y_0.85VO₄ crystal is an excellent laser medium for doubly QML lasers.     

Performance comparisons of passively Q-switched intracavity-frequency-doubled Nd:Gd<Subscript>0.19</Subscript>Y<Subscript>0.81</Subscript>VO<Subscript>4</Subscript> and Nd:Gd<Subscript>0.83</Subscript>Y<Subscript>0.17</Subscript>VO<Subscript>4</Subscript> lasers at 671 nm

Performance comparisons of laser-diode pumped passively Q-switched intracavity-frequency-doubled Nd:Gd_0.19Y_0.81VO₄ and Nd:Gd_0.83Y_0.17VO₄ lasers at 671 nm are demonstrated for the first time to our knowledge. KTP crystal is used as the frequency doubling material and V:YAG crystal as the saturable absorber with initial transmission of 89%. The dependences of average output power, pulse width, pulse repetition rate, single-pulse energy and peak power on incident pump power are measured and contrasted. The experimental results show that, Nd:Gd_0.83Y_0.17VO₄ laser has more excellent properties than Nd:Gd_0.19Y_0.81VO₄ laser at 671 nm.     

Investigations of the electron paramagnetic resonance spectra of VO<Superscript>2+</Superscript> in CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The EPR spectra for VO²⁺ in CaO-Al₂O₃-SiO₂ system are calculated using complete diagonalization method (CDM) and perturbation theory method (PTM). The calculated results are in good agreement with the observed values. By comparing the calculated results by CDM and PTM in a wide range of crystal field parameters, the validity of the PTM formulas has been studied. It is shown that, the PTM formulas are reasonable and reliable in a wide range of CF parameters.     

Crystal growth,spectroscopic characterization and laser performance of Nd:Lu<Subscript>0.33</Subscript>Y<Subscript>0.36</Subscript>Gd<Subscript>0.3</Subscript>VO<Subscript>4</Subscript> crystal

A new three-matrix mixed vanadate crystal Nd:Lu_0.33Y_0.36Gd_0.3VO₄ (Nd:LuYGdVO₄) crystal was grown by the Czochralski method. Room temperature absorption and fluorescence spectra of the Nd:LuYGdVO₄ crystals were measured and the spectroscopic parameters were calculated by the Judd-Ofelt theory. The intensity parameters of the Nd:LuYGdVO₄ crystal were Ω₂ = 9.736 × 10⁻²⁰ cm², Ω₄ = 4.179 × 10⁻²⁰ cm², Ω₆ = 8.020 × 10⁻²⁰ cm² and the stimulate emission cross section was 5.3 × 10⁻¹⁹ cm². Diodepumped actively Q-switched and passively Q-switched Nd:LuYGdVO₄ and Nd:Lu_0.14Y_0.86VO₄ lasers at 1.06 μm were demonstrated. The results indicate that, for both actively and passively Q-switched lasers, the Nd:LuYGdVO₄ lasers can generate shorter pulse width with higher peak power than the Nd:Lu_0.14Y_0.86VO₄ lasers at the same cavity conditions.     

Improved photoluminescence of pulsed-laser-ablated Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>VO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> thin film phosphors by Gd substitution

Gd-substituted Y_1-xGd_xVO₄:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed-laser deposition. The films grown under different deposition conditions have been characterized using microstructural and luminescent measurements. The crystallinity, surface morphology, and photoluminescence (PL) of the films are highly dependent on the amount of Gd. The photoluminescence (PL) brightness data obtained from Y_1-xGd_xVO₄:Eu³⁺ films grown under optimized conditions have indicated that the PL brightness is more dependent on the surface roughness than the crystallinity of the films. In particular, the incorporation of Gd into the YVO₄ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_0.57Gd_0.40Eu_0.03VO₄ thin film whose brightness was increased by a factor of 2.5 and 1.9 in comparison with that of YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films, respectively. This phosphor have application to flat panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Hydrothermal route to VO<Subscript>2</Subscript> (B) nanorods: controlled synthesis and characterization

One-dimensional vanadium dioxides have attracted intensive attention owing to their distinctive structure and novel applications in catalysis, high energy lithium-ion batteries, chemical sensors/actuators and electrochemical devices etc. In this paper, large-scale VO₂ (B) nanorods have been successfully synthesized via a versatile and environment friendly hydrothermal strategy using V₂O₅ as vanadium source and carbohydrates/alcohols as reductant. The obtained samples are characterized by XRD, FT-IR, TEM, and XPS techniques to investigate the effects of chemical parameters such as reductants, temperature, and time of synthesis on the structure and morphology of products. Results show that pure B phase VO₂ with homogeneous nanorod-like morphology can be prepared easily at 180 °C for 3 days with glycerol as reluctant. Typically, the nanorod-like products are 0.5–1 μm long and 50 nm width. Furthermore, it is also confirmed that the products are consisted of VO₂, corresponding to the B phase. More importantly, this novel approach is efficient, free of any harmful solvents and surfactants. Therefore, this efficient, green, and cost-saving route will have great potential in the large-scale fabrication of 1D VO₂ (B) nanorods from the economic and environmental point of view.     

Disintegration of a coarse-grained vanadium monoxide VO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> powder

A coarse-grained powder of nonstoichiometric cubic vanadium monoxide VO _y is disintegrated in a Retch PM 200 planetary ball mill. Milling of the coarse-grained vanadium monoxide powder VO _y at a rate of rotation of 500 rpm for 2 h significantly broadens diffraction lines, and the crystal structure of vanadium monoxide VO_1.00 after milling remains the same. High-resolution scanning electron microscopy and X-ray diffraction studies of the microstructure of vanadium monoxide demonstrate that high-energy milling can produce vanadium monoxide powders with an average crystallite size of 23 ± 10 nm. The vanadium monoxide produced by milling has a crystallite size that is half the crystallite size in the titanium monoxide produced by severe plastic deformation.     

Efficient Nd:Y<Subscript>0.36</Subscript>Gd<Subscript>0.64</Subscript>VO<Subscript>4</Subscript>-GdCa<Subscript>4</Subscript>O(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> red laser under diode pumping into the emitting level

We report a red laser at 671 nm generation by intracavity frequency doubling of a continuous wave (cw) laser operation of a 1342 nm Nd:Y_0.36Gd_0.64VO₄ laser under diode pumping into the emitting level ⁴ F _3/2. An GdCa₄O(BO₃)₃ (GdCOB) crystal, cut for critical type I phase matching at room temperature is used for second harmonic generation of the laser. At an incident pump power of 17.8 W, as high as 1.12 W of cw output power at 671 nm is achieved. The optical-to-optical conversion efficiency is up to 6.3%, and the fluctuation of the red output power was better than 3.5% in the given 30 min.     

Passively Q-switched laser performance of a diode-pump mixed Nd:Lu<Subscript>0.15</Subscript>Y<Subscript>0.85</Subscript>VO<Subscript>4</Subscript> crystal

A diode-pumped passively Q-switched Nd:Lu_0.15Y_0.85VO₄ laser with a GaAs output coupler is demonstrated. By using a mixed crystal Nd:Lu_0.15Y_0.85VO₄ as laser medium, the passively Q-switched laser can generate shorter pulse width with higher peak power in comparison with the passively Q-switched Nd:LuVO₄ or Nd:YVO₄ lasers under the same laser cavity. At the incident pump power 11.9 W, the minimum pulse width of 3.23 ns and the maximum peak power 1.67 kW can be obtained. The average output power and the pulse repetition rate of the laser are also measured. The experimental results show that the mixed crystal is a promising laser medium for shorter Q-switched pulse with higher peak power.     

Quasi-three-level laser operation of Nd:Y<Subscript>0.53</Subscript>Gd<Subscript>0.47</Subscript>VO<Subscript>4</Subscript> mixed vanadate crystal oscillating at 913 nm

Efficient continuous-wave (CW) laser operation on the ⁴ F _3/2 → ⁴ I _9/2 transition of Nd:Y_0.53Gd_0.47VO₄, a mixed vanadate crystal, is demonstrated at room temperature employing a compact plano-concave resonator, generating a polarized output power of 0.39 W at 913.2 nm with 2.85 W of pump power absorbed, the optical-to-optical and slope efficiencies being 14 and 25%, respectively.     

Crystal and magnetic structure of CeVO<Subscript>3</Subscript>

The crystal structure and the magnetic ordering pattern of the electrically insulating perovskite CeVO₃ was investigated by high-resolution powder X-ray diffraction and single-crystal neutron diffraction. A structural phase transition from an orthorhombic to a monoclinic structure (with space groups Pbnm and P2₁/b, respectively) was observed upon cooling below T _s = 136 K. This transition is associated with a strong distortion of the VO₆-octahedra and can be attributed to orbital ordering. A magnetic ordering transition driven by exchange interactions between vanadium moments is observed at T _N = 124 K, and antiferromagnetic interactions between magnetic moments on vanadium and cerium ions induce a progressive magnetic polarization of the cerium sublattice at lower temperatures. The full magnetic structure is described by a superposition of the modes (C _x , F _y , −) and (F _x , C _y , −). The unit cell volume and the tilt angles of the VO₆-octahedra in the CeVO₃-crystal structure are anomalous compared to those of other members of the series RVO₃ (R = lanthanide atom), and the ordered magnetic moments on both vanadium and cerium sublattices at low temperatures are considerably smaller than the free-ion values of V³⁺ and Ce³⁺. Possible origins of this behavior are discussed.     

All-solid-state Nd:Gd<Subscript>0.18</Subscript>Y<Subscript>0.82</Subscript>VO<Subscript>4</Subscript>-LBO green laser at 532 nm

We report a continuous-wave (CW) coherent green radiation at 532 nm by intracavity frequency doubling generation of 1064 nm Nd:Gd_0.18Y_0.82VO₄ laser. With incident pump power of 18.2 W, output power of 1.08 W at 532 nm has been obtained using a 5 mm-long KTP crystal. The optical conversion efficiency was up to 5.9%. At the output power level of 1.08 W, the output stability is better than 5%. The beam quality M² values were equal to 1.26 and 1.12 in X and Y directions, respectively.     

Diode-pumped passively Q-switched and mode-locked Nd:Lu<Subscript>0.15</Subscript>Y<Subscript>0.85</Subscript>VO<Subscript>4</Subscript> laser with a GaAs saturable absorber

By using a-cut Nd:Lu_0.15Y_0.85VO₄ mixed crystal as laser gain medium, a diode-pumped passively Q-switched and mode-locked (QML) laser with a GaAs saturable absorber in a Z-type folded cavity is demonstrated for the first time. The Q-switched mode-locked laser pulses with about 90% modulation depth are obtained as long as the pump power reached the oscillation threshold. The repetition rate of the passively Q-switched pulse envelope ranges from 50 to 186 kHz as the pump power increases from 0.915 to 6.520 W. Under an incident pump power of 6.52 W, the QML pulses with the largest average output power of 694 mW, the shortest pulse width of 200 ns and the highest pulse energy of 3.73 μJ are obtained. The mode-locked pulse width inside the Q-switched envelope is estimated to be about 275 ps. The experimental results show that Nd:Lu_0.15Y_0.85VO₄ is a promising mixed crystal for QML laser.     

On the Optical Properties of Thin‐Film Vanadium Dioxide from the Visible to the Far Infrared

The insulator‐to‐metal transition (IMT) in vanadium dioxide (VO₂) can enable a variety of optics applications, including switching and modulation, optical limiting, and tuning of optical resonators. Despite the widespread interest in VO₂ for optics, the wavelength‐dependent optical properties across its IMT are scattered throughout the literature, are sometimes contradictory, and are not available at all in some wavelength regions. Here, the complex refractive index of VO₂ thin films across the IMT is characterized for free‐space wavelengths from 300 nm to 30 µm, using broadband spectroscopic ellipsometry, reflection spectroscopy, and the application of effective‐medium theory. VO₂ films of different thicknesses are studied, on two different substrates (silicon and sapphire), and grown using different synthesis methods (sputtering and sol–gel). While there are differences in the optical properties of VO₂ synthesized under different conditions, these differences are surprisingly small in the ≈2–11 µm range where the insulating phase of VO₂ also has relatively low optical loss. It is anticipated that the refractive‐index datasets from this article will be broadly useful for modeling and design of VO₂‐based optical and optoelectronic components, especially in the mid‐wave and long‐wave infrared.     

Comparison of VO<Subscript>2</Subscript> thin films prepared by inorganic sol-gel and IBED methods

VO₂ thin films with semiconductor-to-metal phase-transition properties were prepared by inorganic sol-gel and IBED (ion-beam-enhanced deposition) methods on SiO₂/Si substrate. The crystalline phase and the shape and width of the hysteresis curves of these VO₂ films were significantly different. For sol-gel VO₂ films, the transition started at close to 62 °C upon heating. The temperature interval needed to complete the phase transition was 8 °C, the ratio of resistance (R_{20 °C}/R_{80 °C}) reached three orders and the hysteresis width was 6 °C. However, the IBED film post-annealed in Ar at 700 °C underwent a phase transition from 45 °C to 80 °C, the ratio of resistance was more than two orders and the hysteresis width was 2 °C. In addition, the TCR (temperature coefficient of resistance) at 22 °C of the IBED film was 3.5%/K, much larger than the 0.7%/K TCR of the sol-gel film. PACS 73.50.F; 73.66.E; 81.20; 81.05.Z; 81.15