Structural transformations in MoO<Subscript>x</Subscript> thin films grown by pulsed laser deposition

In this work, laser-induced crystallization in MoO_x thin films (1.8x2.1) is reported. This transformation involves a MoO_x oxidation and subsequently a crystallization process from amorphous MoO₃ to crystalline MoO₃. For comparison purposes crystallization is induced thermally, in an oven, as well. The crystallization kinetics is monitored by Raman spectroscopy; a threshold in the energy density necessary to induce the phase transformation is determined in the case of photo-crystallization. This threshold depends on the type of substrate on which the film is deposited. For the thin films deposited on glass substrates, the structural transformation is from amorphous MoO_x to the thermodynamically stable MoO₃ crystalline phase. For the thin films deposited on Si(100) the structural transformation is from amorphous MoO_x to a mixture of MoO₃ and the thermodynamically unstable MoO₃ crystalline phases. The structural transformations are also characterized by scanning electron microscopy and light-transmission experiments. PACS 81.15.Fg; 61.80.Ba; 78.30.-j     

Submicron Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript> material prepared by rheological phase method and its evaluation of lithium storage performances

In this paper, submicron Li₂MoO₄ material was synthesized via rheological phase method. The structure, composition and morphology of the obtained powders were characterized by X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS) and scanning electron microscope (SEM), respectively. The key calcination temperature was 700 ^oC. The particle sizes were about from 100 to 300 nm. As anode material of lithium ion batteries, lithium storage performances of the as-prepared Li₂MoO₄ were evaluated at different current densities. The best capacity retention was 75.7% of the initial capacity (592.13 mAh g^-1) after 50 cycles at 0.2 mA cm^-2 in 0.1-2.5 V, and the resistance was about 123.5 Ω, indicating a potential prospect in the application of lithium ions batteries.     

Lithiated c-V<Subscript>2</Subscript>O<Subscript>5</Subscript> thin-film as positive electrode for rocking-chair solid-state lithium microbattery

We report for the first time the use of lithiated crystalline V₂O₅ thin films as positive electrode in all-solid-state microbatteries. Crystalline Li_xV₂O₅ films (x ≈ 0.8 and 1.5) are obtained by vacuum evaporation of metallic lithium deposited on sputtered c-V₂O₅. An all-solid-state lithium microbattery of Li_1.5V₂O₅/LiPON/Li exhibited a typical reversible capacity of 50 μAh/cm² in the potential range 3.8/2.15 V which exceeds by far the results known on all-solid-state lithium batteries using amorphous V₂O₅ films and lithiated amorphous Li_xV₂O₅ thin films as positive electrode. Hence, the present work opens the possibility of using high performance crystalline lithiated V₂O₅ thin films in rocking-chair solid-state microbatteries.     

Highly efficient solid-state synthesis of carbon-encapsulated ultrafine MoO<Subscript>2</Subscript> nanocrystals as high rate lithium-ion battery anode

A simple and highly efficient method is developed for the one-step in situ preparation of carbon-encapsulated MoO₂ nanocrystals (MoO₂@C) with core-shell structure for high-performance lithium-ion battery anode. The synthesis is depending on the solid-state reaction of cyclopentadienylmolybdenum tricarbonyl dimer with ammonium persulfate in an autoclave at 200 °C for 30 min. The large amount of heat generated during the explosive reaction cleaves the cyclopentadiene ligands into small carbon fragments, which form carbon shell after oxidative dehydrogenation coating on the MoO₂ nanocrystals, resulting in the formation of core-shell structure. The MoO₂ nanocrystals have an equiaxial morphology with an ultrafine diameter of 2–8 nm, and the median size is 4.9 nm. Hundreds of MoO₂ nanocrystals are encapsulated together by the worm-like carbon shell, which is amorphous and about 3–5 nm in thickness. The content of MoO₂ nanocrystals in the nanocomposite is about 69.3 wt.%. The MoO₂@C anode shows stable cyclability and retains a high reversible capacity of 443 mAh g^?1 after 50 cycles at a current density of 3 A g^?1, owing to the effective protection of carbon shell.     

Red,Yellow, Blue and Green Emission from Eu<Superscript>3+</Superscript>, Dy<Superscript>3+</Superscript> and Bi<Superscript>3+</Superscript> Doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>nano-Phosphors

Rare earth elements (RE = Eu³⁺& Dy³⁺)and Bi³⁺ doped Y₂O₃ nanoparticles were synthesized by urea hydrolysis method in ethylene glycol, which acts as reaction medium as well as a capping agent, at a low temperature of 140 °C,followed by calcination of the obtained product. Transmission electron microscope (TEM) images reveals that ovoid shaped Y₂O₃ nanoparticles of around 22–24 nm size range were obtained in this method. The respective RE and Bi³⁺ doped Y₂O₃ precursor nanoparticles when heated at 600 and 750 °C, retains the same shape as that of the as-synthesized Y₂O₃ precursor samples. From EDAX spectra, the incorporation of RE ions into the host has been studied. XRD pattern reveals the crystalline nature of the heated nanoparticles and indicate the absence of any impurity phase other than cubic Y₂O₃.However, the as-synthesized nanoparticles were highly amorphous without the presence of any sharp XRD peaks. Photoluminescence study suggests that the synthesized samples could be used as red (Eu³⁺), yellow (Dy³⁺), blue and green (Bi³⁺)emitting phosphors.     

Spectral properties of a Nd<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>Ba<Subscript>2</Subscript>Gd<Subscript>3</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>8</Subscript> crystal

The spectral properties of a promising laser material, ternary molybdate Li₃Ba₂Gd₃(MoO₄)₈:Nd³⁺, are studied (i.e., its optical absorption spectra, luminescence spectra, kinetic of luminescence decay, and temperature dependence of luminescence). Luminescence of the crystalline matrix is detected, and the temperature dependence of its intensity and reabsorption by neodymium are investigated.     

Cooperative down-conversion of UV light in disordered scheelitelike Yb-doped NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> and NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

Concentration series of disordered scheelitelike Yb:NaGd(MoO₄)₂ and Yb:NaLa(MoO₄)₂ single crystals are grown by the Czochralski method. The actual concentrations of Yb³⁺ ions in the crystals are determined by optical-absorption spectroscopy. The luminescence of Yb³⁺ ions in these crystals in the region of 1 μm is studied under UV and IR excitation. In the case of UV excitation, this luminescence appears as a result of nonradiative excited state energy transfer from donor centers of unknown nature to ytterbium. The character of the concentration dependence of Yb³⁺ luminescence indicates that the energy transfer at high Yb concentrations occurs with active participation of a cooperative mechanism, according to which the excitation energy of one donor center is transferred simultaneously to two Yb³⁺ ions. In other words, the quantum yield of this transfer exceeds unity, which can be used to increase the efficiency of crystalline silicon (c-Si) solar cells.     

Photoaccumulating film systems based on TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript> and TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript>:V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanoheterostructures

The thin-film photocatalysts TiO₂/MoO₃ and TiO₂/MoO₃:V₂O₅ obtained by a combination of sol–gel and sintering techniques were studied using the photooxidation of probing dyes, EPR spectroscopy, X-ray diffraction analysis, and electron microscopy. It was shown that due to charge accumulation caused by UV irradiation, these photocatalysts retain their oxidative activity and ability for self-sterilization in the dark for a long time after irradiation was terminated (up to 5 h for TiO₂/MoO₃:V₂O₅).     

Regular hexagonal MoS<Subscript>2</Subscript> microflakes grown from MoO<Subscript>3</Subscript> precursor

Regular hexagonal MoS₂ microflakes with high yield were grown from MoO₃ precursor by a sulfurization process using S powders as sulfuration reducer. The precursors, long and smooth MoO₃ microbelts, were synthesized through a direct oxidation reaction of Mo plates in air. X-ray powder diffraction and scanning electron microscopy revealed that the sulfurized products were hexagonal MoS₂ with regular hexagonal flake-like morphology. The results of transmission electron microscopy examinations demonstrated that the microflakes were single crystalline MoS₂. Elemental analysis by EDAX and XPS showed that the microflakes consist of Mo and S with the atomic ratio near to 0.5. Factors influencing the formation of the product were systematically studied. PACS 81.15.Gh; 81.15.Kk; 81.05.Hd; 78.67.Pt; 82.40.Ck     

CoMoS<Subscript>4</Subscript> Nanoflowers as Anode for Secondary Lithium Batteries

CoMoS₄ nanoflowers was synthesized by precipitation method from Na₂MoO₄, CoCl₂ · 6H₂O and CH₃CSNH₂ as starting materials. X-ray diffraction (XRD) analysis showed that the prepared samples is amorphous structure, X-ray photoelectron spectrometer data of Co, Mo and S in CoMoS₄ revealed that the valences of the corresponding elements are almost +2, +6, and −2, respectively. Scanning electron microscope gave the result that the morphologies of the as-prepared powder is flower-like nanostructure. Moreover, electrochemical tests were also carried out, the initial discharge was 1547 mA h g⁻¹, even after 20 cycles, it still remains 461 mA h g⁻¹.     

Characterization of MoO<Subscript>3</Subscript> nanobelt cathode for Li-battery applications

Molybdenum trioxide (MoO₃) and PPy_xMoO₃ (x=0.5 and 1) nanobelts were obtained by the simple hydrothermal process from MoO₃ sol. The morphology and structure of the samples were characterized using X-ray diffractometry (XRD), Fourier transformation infrared spectroscopy (FTIR), Raman spectra, SEM and AFM. The results show that the H atoms in polypyrrole are H-bonded with the O atoms in the Mo=O bonds of MoO₃ nanobelts. Using the electrolyte, we fabricated electrochemical cells with a configuration of Li/(LiPF₆+EC+DMC)/(MoO₃+acetyleneblack+PTFE) and studied discharge profiles. PACS 81.07.BC; 81.05.Je; 82.47.Aa; 82.45.Fk; 82.45.Gj     

Color-neutral switchable mirrors based on magnesium-titanium thin films

In an investigation of smart-window applications of switchable mirror thin films, Pd-capped magnesium-titanium thin films were prepared by dc magnetron sputtering. Their optical properties, switching durability and crystalline structures have been investigated. We show that Pd/Mg-Ti thin films with specific thicknesses are completely color-neutral in the transparent state and their optical switching properties are suitable for building and automobile window glass applications. The ternary hydrides of Mg_(1-x)Ti_x thin films with Pd overlayers are identified by in situ X-ray diffraction measurements during a hydrogen gas loading of 4%. Pd/Mg_(1-x)Ti_x thin film switchable mirrors show fast hydriding and dehydriding kinetics as compared to a Pd-capped pure Mg thin film due to the catalytic role of doped metallic Ti. PACS 75.20.En; 78.20.-e; 78.70.Ck; 42.70.-a     

LiFePO<Subscript>4</Subscript>/C with high capacity synthesized by carbothermal reduction method

The olivine-type LiFePO₄/C cathode materials were prepared via carbothermal reduction method using cheap Fe₂O₃ as raw material and different contents of glucose as the reducing agent and carbon source. Their structural and morphological properties were investigated by X-ray diffraction, scanning electron microscope, transmission electron microscope, and particle size distribution analysis. The results demonstrated that when the content of the carbon precursor of glucose was 16 wt.%, the synthesized powder had good crystalline and exhibited homogeneous and narrow particle size distribution. Even and thin coating carbon film was formed on the surface of LiFePO₄ particles during the pyrolysis of glucose, resulting in the enhancement of the electronic conductivity. Electrochemical tests showed that the discharge capacity first increased and then decreased with the increase of glucose content. The optimal sample synthesized using 16 wt.% glucose as carbon source exhibited the highest discharge capacity of 142 mAh g⁻¹ at 0.1C rate with the capacity retention rate of 90.4% and 118 mAh g⁻¹ at 0.5C rate.     

A facile synthesis about amorphous CoS<Subscript>2</Subscript> combined with first principle analysis for supercapacitor materials

The structure and electrochemical properties of amorphous CoS₂ and crystalline CoS₂ have been studied with both experimental characterization and theoretical calculations. In the field of experimental characterization, a facile chemical precipitation method is used to synthesize amorphous and crystalline CoS₂ samples with calcining temperatures of 200 and 280 °C, respectively. Comparing with crystalline CoS₂, amorphous structure of CoS₂ manifests great electron conductivity, effective porous structure, and exhibit a high specific capacitance of 996.16 F g^?1 at current density of 0.5 A g^?1, excellent rate capability of 89.8% retention with the current density ranging from 0.5 to 5 A g^?1, and a great cycling stability of 97.6% retention after 10,000 cycles at 2 A g^?1 in 6 mol L^?1 KOH aqueous electrolyte. In the area of theoretical calculation, we used the first principle and obtained the band structure with band gap of 0.00369 eV and DOSs with high locality of D-orbital from 69.88689 electrons/eV main peak, in the CoS₂ amorphous. The result confirms that amorphous CoS₂ have higher conductivity than crystalline CoS₂ in theory. In addition, the as-assembled asymmetric supercapacitor of Co-S-200//AC also exhibits the maximum specific capacitance of 104 F g^?1 within a cell voltage from 0 to 1.5 V at current density of 0.5 A g^?1 and indicates a great cycling stability of 95.68% and excellent capacitance behavior. All results demonstrate a great potential of amorphous CoS₂ active material for supercapacitors.     

Magnetotransport properties of nano-constriction array in La<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> film

Nano-constriction array in La_0.67Sr_0.33MnO₃ film was fabricated by using ion beam etching masked by a monolayer of packed and ordered array of SiO₂ microspheres. Nano-constrictions of around 50 nm in width were fabricated. The low field magnetoresistance (LFMR) exhibited in the samples were observed to be current dependent and the I-V characteristics of the film were found to be nonlinear. These observations were attributed to the co-existence of the ferromagnetic regions and the nano-constricted region of weakened ferromagnetic coupling where Mn³⁺-O-Mn⁴⁺ bond were distorted due to the ion beam bombardment. The spin polarized bias current would strengthen local ferromagnetic coupling when passing through this nano-constricted regions. This current effect is relatively large comparing to the external magnetic field to the drop of resistance.     

Photoconductivity studies on amorphous and crystalline TiO<Subscript>2</Subscript> films doped with gold nanoparticles

In this work, amorphous and crystalline TiO₂ films were synthesized by the sol–gel process at room temperature. The TiO₂ films were doped with gold nanoparticles. The films were spin-coated on glass wafers. The crystalline samples were annealed at 100°C for 30 minutes and sintered at 520°C for 2 h. All films were characterized using X-ray diffraction, transmission electronic microscopy and UV-Vis absorption spectroscopy. Two crystalline phases, anatase and rutile, were formed in the matrix TiO₂ and TiO₂/Au. An absorption peak was located at 570 nm (amorphous) and 645 nm (anatase). Photoconductivity studies were performed on these films. The experimental data were fitted with straight lines at darkness and under illumination at 515 nm and 645 nm. This indicates an ohmic behavior. Crystalline TiO₂/Au films are more photoconductive than the amorphous ones.     

Gas sensing properties of MoO<Subscript>3</Subscript> nanoparticles synthesized by solvothermal method

MoO₃ nanoparticles were prepared by thermally oxidizing the MoO₂ nano-crystallites synthesized by solvothermal reaction, and their gas sensing properties were investigated. Ethanol and water mixed solvents were used in the solvothermal synthesis, and it was observed that the phase, size, and morphology of the products were strongly dependent on the composition of solvents. Well-crystallized and spherical MoO₂ nano-crystallites (~20 nm) were obtained in the mixed solvent (water:ethanol = 40:10 in vol), and subsequent heat treatment at 450 °C produced the well-separated, slightly elongated MoO₃ nano-particles of ~100 nm. The nano-particle MoO₃ gas sensor responded to both oxidizing and reducing gases, but it exhibited the extremely high gas response toward H₂S with a short response time (<10 s). In particular, the magnitude of gas response of nano-particle MoO₃ gas sensor was about 10 times higher than that of micron-sized commercial MoO₃ powder sensor at 20 ppm H₂S.     

Nonlinear optical characterization of LaEr(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> thin films using the <Emphasis Type="BoldItalic">Z</Emphasis> -scan technique

The nonlinear optical properties of thin films of LaEr(MoO₄)₃ were studied using a ∼30 ps Nd:YAG laser at 532 nm with a repetition rate of 250 Hz. Closed aperture Z-scan measurement revealed a negative nonlinearity in the LaEr(MoO₄)₃. The nonlinear refractive index γ=1.38×10^-10 cm²/W and nonlinear absorption coefficient β=16.8×10^-6 cm/W were calculated from the Z-scan data. The fluorescent upconversion spectra were recorded with 980 nm excitation. An optical switching mechanism based on nonlinear absorption is also presented experimentally. PACS 81.15.Fg; 77.84.Bw; 33.50.Dq; 42.70.Mp     

Optical and electrical properties of nanocrystalline TiO<Subscript>2</Subscript>:Pd semiconducting oxides

Electrical and optical properties of TiO₂:Pd thin films deposited from Ti-Pd mosaic targets sputtered in reactive oxygen plasma have been studied. The properties were investigated for thin films with the Pd amount of 5.5 at. %, 8.4 at. % and 23 at. %. Based on resistivity measurements a drop from 10³ down to almost 10⁻³Ωcm has been recorded when the Pd amount was varied from 5.5 at. % to 23 at. %, respectively. Moreover, it was shown that doping with different amounts of Pd results in the possibility of obtaining both types of electrical conduction: n-type for the TiO₂ with 5.5 at. % and 8.4 at. % of Pd and p-type for the TiO₂ with 23 at. % of Pd thin films. From optical measurements it has been found that as the Pd amount was increased the transmission through the thin films was reduced and position of the fundamental absorption edge was shifted toward a longer wavelength range of up to 600 nm. The optical band gap was calculated for direct and indirect transitions from optical absorption spectra. Structural properties were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The XRD patterns displayed occurrence of the crystalline, TiO₂-rutile for lower Pd amounts (5.5 at. %, 8.4 at. %), while the TiO₂:Pd (23 at. %) thin films displayed XRD-amorphous behaviour. Images obtained from AFM displayed dense, nanocrystalline structure with homogenous distribution of crystallites. Additionally performed secondary ion mass spectroscopy investigation confirmed homogenous distribution of Pd in the whole thickness of the prepared thin films.     

Mo nitrides and carbonitrides via metallic phase transition of MoO3 films using ammonium salt precursors in chemical vapor deposition

Transition-metal-based nitrides and carbides have been widely studied for various applications because of their excellent mechanical, electrical, and catalytic properties. Although outstanding performances of Mo nitride and carbonitride synthesized by chemical reaction methods have been reported recently for catalytic applications, a metallic phase transition method for pre-deposited MoO₃ precursor films, which is suitable for application to Si or metallic substrates, has rarely been reported. Herein, we investigate Mo nitride and carbonitride thin films synthesized via nitriding and carbonitriding of MoO₃ films using two types of ammonium salt precursors, urea and ammonium carbonate (AC), in the chemical vapor deposition (CVD) process. The phase-changed crystalline films of Mo carbonitride via the urea reaction and Mo nitride via the AC reaction were determined to be MoC_0.5N_0.5 and MoN by X-ray diffractometry, respectively. Nevertheless, amorphous states of carbons and their related compounds, unreacted residual MoO₃, and incompletely reacted MoO₂ remained in the films, as determined by other thin film analyses. When the residual MoO₂ was minimal, the films exhibited the lowest electrical resistivity, i.e., ∼10⁻⁴ Ω·cm for Mo carbonitride and ∼10⁻³ Ω·cm for Mo nitride, implying an optimum metallic phase transition. Our results pave the way for the nitriding and carbonitriding of transition metal oxides using ammonium salt precursors for a one-step reaction in the CVD process.