Reducing and tuning the work function of field emission nanocomposite CNT/NiO cathodes by modifying the chemical composition of the oxide.

This work presents for the first time the possibility of reducing and tuning the work function of field emission cathodes coated with metal oxides by changing the chemical composition of oxide coatings using an example of heat-treated CNT/NiO nanocomposite structures. These cathodes are formulated using carbon nanotube (CNT) arrays that are coated with ultrathin layers of nickel oxide (CNT/NiO) by atomic layer deposition (ALD). It was found that NiO at thicknesses of several nanometers grown on CNTs heat treated at a temperature of 350 °C can change its stoichiometric composition towards the formation of oxygen vacancies, since the Ni3+/Ni2+ peak area ratio increases and the position of the Ni-O peak binding energies shifts as observed using X-ray photoelectron spectroscopy (XPS). According to the secondary electron cut-off, the work function was 4.95 for pristine CNTs and it was found that the work function of deposited NiO layers on CNTs decreased after heat treatment. The decrease in work function occurs as a result of changes in the chemical composition of the oxide film. For the heat-treated CNT/NiO composites, the work function was 4.30 eV with a NiO layer thickness of 7.6 nm, which was less than that for a NiO thin film close to the stoichiometric composition, which had a work function of 4.48 eV. The field emission current-voltage characteristics showed that the fields for producing an emission current density of 10 µA cm-2 were 5.54 V µm-1 for pure nanotubes and 4.32 V µm-1 and 4.19 V µm-1 for NiO-coated CNTs (3.8 and 7.6 nm), respectively. The present study has shown that heat treatment of deposited thin NiO layers on field cathodes is a promising approach to improve the efficiency of field emission cathodes and is a new approach in vacuum nanoelectronics that allows tuning the work function of field emission cathodes.

The Valence Band Structure of the [Ni(Salen)] Complex: An Ultraviolet, Soft X-ray and Resonant Photoemission Spectroscopy Study.

The valence band photoemission (VB PE) spectra of the [Ni(Salen)] molecular complex were measured by ultraviolet, soft X-ray and resonant photoemission (ResPE) using photons with energies ranging from 21.2 eV to 860 eV. It was found that the Ni 3d atomic orbitals' (AOs) contributions are most significant for molecular orbitals (MOs), which are responsible for the low-energy PE band at a binding energy of 3.8 eV in the VB PE spectra. In turn, the PE bands in the binding energies range of 8-16 eV are due to the photoionization of the MOs of the [Ni(Salen)] complex with dominant contributions from C 2p AOs. A detailed consideration was made for the ResPE spectra obtained using photons with absorption resonance energies in the Ni 2p3/2, N 1s, and O 1s Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra. A strong increase in the intensity of the PE band ab was found when using photons with an energy 854.4 eV in the Ni 2p3/2 NEXAFS spectrum. This finding is due to the high probability of the participator-Auger decay of the Ni 2p3/2-13d9 excitation and confirms the relationship between the PE band ab with the Ni 3d-derived MOs.

Cu, Mg Codoped Bismuth Tantalate Pyrochlores: Crystal Structure, XPS Spectra, Thermal Expansion, and Electrical Properties.

The pyrochlore-type solid-solution formation in a Bi1.6Mg0.8-xCuxTa1.6O7.2-Δ system, synthesized for the first time, is observed at x ≤ 0.56. High-temperature X-ray diffraction showed that the pyrochlore phase exists in air up to 1080 °C, where its thermal decomposition leads to the segregation of (Mg,Cu)Ta2O6. The thermal expansion coefficients of the end member, Bi1.6Mg0.24Cu0.56Ta1.6O7.2-Δ, increase from 3.3 × 10-6 °C-1 at room temperature up to 8.7 × 10-6 °C-1 at 930 °C. Rietveld refinement confirmed that the pyrochlore crystal structure is disordered with space group Fd3̅m:2 (Z = 8, no. 227). Doping with copper results in a modest expansion of the cubic unit cell, promotes sintering of the ceramic materials, and induces their red-brown color. X-ray photoelectron spectroscopy demonstrated that the states of Bi(III) and Mg(II) are not affected by doping, and the effective charge of tantalum cations is lower than +5, while the Cu(II) states coexist with Cu(I). The electron spin resonance spectra display a single line with g = 2.2, ascribed to the dipole-broadened Cu2+ signal. The dielectric permittivity of Bi1.6Mg0.8-xCuxTa1.6O7.2-Δ ceramics may achieve up to ∼105, with the dielectric loss tangent varying in the range from 0.2 up to 12. Multiple dielectric relaxations are found at room temperature and above for all samples.

Novel Ni-Doped Bismuth-Magnesium Tantalate Pyrochlores: Structural and Electrical Properties, Thermal Expansion, X-ray Photoelectron Spectroscopy, and Near-Edge X-ray Absorption Fine Structure Spectra.

The samples of Ni-doped bismuth magnesium tantalate pyrochlores with the general formula Bi1.4(Mg1-x Ni x )0.7Ta1.4O6.3 (x = 0.3, 0.5, 0.7) were obtained by solid-phase synthesis. The crystal structure of the pyrochlore type (sp. gr. Fd3̅m:2) was clarified by the Rietveld method on the basis of X-ray powder diffraction data. The unit cell parameters increase with the decreasing nickel content in the range from 10.5319(1) to 10.5391(1) Å. The electronic state of atoms is established by the XPS method. According to XPS analysis, bismuth atoms have an effective charge of +3, nickel atoms +(2 + δ), and tantalum ions +(5 - δ). The coefficient of thermal expansion of the lattice of the samples was calculated from high-temperature X-ray structural measurements in the range of -180 to 1050 °C. The average values of linear TECs α in the temperature ranges of 30-570 and 600-1050 °C are 5.1 × 10-6 and 8.1 × 10-6 °C-1, respectively. The monotonicity of the change in the thermal expansion coefficient in the temperature range from -100 to 1050 °C indicates the absence of phase transformations. All samples are dielectric and exhibit high activation energies ∼2.0 eV, moderately high dielectric constants ∼24-28, and tangent dielectric losses ∼0.002 at 1 MHz and 21 °C. The electrical properties of the samples are described by a simple parallel equivalent scheme. The chemical composition of the materials has little effect on the polarizability of the medium or on the value of the activation energy of the conductivity. Ionic processes in investigated materials at frequencies 200-106 Hz and at temperatures 100-450 °C were not detected.

Thermal Expansion, XPS Spectra, and Structural and Electrical Properties of a New Bi2NiTa2O9 Pyrochlore.

A phase-pure nickel bismuth tantalate with pyrochlore structure was synthesized by a solid-phase synthesis method for the first time. The crystal structure of pyrochlore (refined formula Bi1.58Ni0.60Ta1.40O7, sp. gr. Fd-3m, a = 10.5343 Å, Z = 8) was clarified by the Rietveld method on the basis of X-ray powder diffraction (XRD) data. The crystallite size determined by the Scherrer method is ∼46 nm. The sample has an atypical pink-purple color. The electronic state of the atoms was investigated by XPS. According to XPS analysis, bismuth atoms have an effective charge of +3; nickel atoms, +(2 + δ); tantalum ions, +(5 - δ). The thermal expansion coefficient of the cell is calculated from high-temperature X-ray measurements in the range of 30-1200 °C. The thermal expansion coefficient (TEC) increases monotonically from 3.79 × 10-6 °C-1 (30 °C) to 8.32 × 10-6 °C-1 (990 °C). Above 1080 °C, the TEC decreases due to the thermal dissociation of pyrochlore with new NiTa2O6 phase formation. Ni-doped bismuth tantalate refers to dielectrics and exhibits a moderately high dielectric constant, ∼32, and low dielectric losses, ∼2 × 10-3 at 1 MHz and ∼30 °C. Above 300 °C, the dielectric losses and dielectric permittivity increase in the low-frequency region due to the activation of oxygen anions. It is found that the electrical characteristics of the sample are significantly affected by the ambient air humidity. An equivalent scheme which satisfactorily describes the electrical properties of the sample has been proposed.

Single Step Laser-Induced Deposition of Plasmonic Au, Ag, Pt Mono-, Bi- and Tri-Metallic Nanoparticles.

Multimetallic plasmonic systems usually have distinct advantages over monometallic nanoparticles due to the peculiarity of the electronic structure appearing in advanced functionality systems, which is of great importance in a variety of applications including catalysis and sensing. Despite several reported techniques, the controllable synthesis of multimetallic plasmonic nanoparticles in soft conditions is still a challenge. Here, mono-, bi- and tri-metallic nanoparticles were successfully obtained as a result of a single step laser-induced deposition approach from monometallic commercially available precursors. The process of nanoparticles formation is starting with photodecomposition of the metal precursor resulting in nucleation and the following growth of the metal phase. The deposited nanoparticles were studied comprehensively with various experimental techniques such as SEM, TEM, EDX, XPS, and UV-VIS absorption spectroscopy. The size of monometallic nanoparticles is strongly dependent on the type of metal: 140-200 nm for Au, 40-60 nm for Ag, 2-3 nm for Pt. Bi- and trimetallic nanoparticles were core-shell structures representing monometallic crystallites surrounded by an alloy of respective metals. The formation of an alloy phase took place between monometallic nanocrystallites of different metals in course of their growth and agglomeration stage.

Interface-Assisted Synthesis of the Mn3-xFexO4 Gradient Film with Multifunctional Properties.

Anisotropic gradient materials are considered as promising and novel in that they have numerous functional properties and are able to transform into hierarchical microstructures. We report a facile method of gradient inorganic thin film synthesis through diffusion-controlled deposition at the gas-solution interface. To investigate the reaction of interfacial phase boundary controllable hydrolysis by gaseous ammonium, an aqueous solution of FeCl3 and MnCl2 was chosen, as the precipitation pH values for the hydroxides of these metals differ gradually. As a result of synthesis using the gas-solution interface technique (GSIT), a thin film is formed on the surface of the solution that consists of Mn2+(Fe,Mn)23+O4 nanoparticles with hausmannite crystal structure. The ratio between iron and manganese in the film can be adjusted over a wide range by varying the synthetic procedure. Specific conditions are determined that allow the formation of a Mn-Fe mixed oxide film with a gradient of composition, morphology, and properties, as well as its further transformation into microscrolls with a diameter of 10-20 µm and a length of up to 300 µm, showing weak superparamagnetic properties. The technique reported provides a new interfacial route for the development of functional gradient materials with tubular morphology.