Luminescence properties of oxide films formed by anodization of aluminum in 12-tungstophosphoric acid

In this paper, we have investigated luminescence properties of oxide films formed by anodization of aluminum in 12-tungstophosphoric acid. For the first time we have measured weak luminescence during anodization of aluminum in this electrolyte (so-called galvanoluminescence GL) and showed that there are wide GL bands in the visible region of the spectrum and observed two dominant spectral peaks. The first one is at about 425 nm, and the second one shifts with anodization voltage. As the anodization voltage approaches the breakdown voltage, a large number of sparks appear superimposed on the anodic GL. Several intensive band peaks were observed under breakdown caused by electron transitions in W, P, Al, O, H atoms. Furthermore, photoluminescence (PL) of anodic oxide films and anodic-spark formed oxide coatings were performed. In both cases wide PL bands in the range from 320 nm to 600 nm were observed.     

Thin-film particles of graphite oxide. 2: Preliminary studies for internal micro fabrication of single particle and carbonaceous electronic circuits

Some preliminary studies to realize a carbonaceous electronic circuit were carried out using the liquid-dispersible thin-film particles of graphite oxide and their conductive reduction product. (1) The affinity of insulator substrates (diamond, silicon carbide, silicon, sapphire and three kinds of glass) for the particles was improved by heating and immersion in water. (2) The electric conductivity was measured for a wide wiring pattern formed by a large number of the reduced thin-film particles mounted on the substrate, and the value was 1600 S/m after heating at 500 °C. (3) To make the prototype of a narrow wiring or a micro device, the internal micro fabrication (position-selective removal) of a single particle was attempted using focused ion beam. Many kinds of patterns which contain narrow wiring having a width of 200 nm etc. were formed in the reduced thin-film particle having about 10 nm thickness. (4) The simple model calculation of anisotropic conductivity was executed for thin graphite which has a small number of layers and finite size. In the case of the fine graphitic carbonaceous devices and circuits, much attention must be paid to their sizes in all directions.     

Film thickness dependence of the dielectric properties of SrTiO3/BaTiO3 multilayer thin films deposited by double target RF magnetron sputtering

Four-layer SrTiO₃/BaTiO₃ thin films ((ST/BT)₄) with various thicknesses deposited on Pt/Ti/SiO₂/Si substrates at 500 °C by double target RF magnetron sputtering have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), profilometry, capacitance-voltage and current-voltage measurements. The XRD patterns reveal the frame formation of the sputter deposited (ST/BT)₄ with controlled modulation. The adhesion between the Pt bottom electrode layer and the BT layer is excellent. The dielectric constant of the (ST/BT)₄ multilayer thin film increases with increasing film thickness. The effects of temperature, frequency, and bias voltage on the dielectric constant of the (ST/BT)₄ multilayer thin films are discussed in detail. The leakage current density of the (ST/BT)₄ multilayer with a thickness of 450.0 nm is lower than 1.0 × 10⁻⁸ A/cm² for the applied voltage of less than 5 V, showing that the multilayer thin films with such a characteristic could be applied for use in dynamic random access memory (DRAMs) capacitors.     

On the contribution of electrostriction to charge-induced stresses in anodic oxide films

Electrostriction has been known for long as a major source of internal stress developing in oxide films during anodising. However, in many studies, the contribution of electrostriction is estimated using an oversimplified equation, leading to a systematic underestimation. In this work, a modified theory is first presented for linking the in-plane electrostriction stress to the applied electric field. The corrected equation explicitly takes into account the dielectric properties of the deformed material through the appropriate electrostriction parameters of the oxide film. A new experimental procedure is then described for measuring electrostriction stresses in situ during anodising, and applied to ultrathin (<100 nm) TiO₂ films. Oxide films were first grown potentiodynamically on one side of cantilevered electrodes. The electric field in the oxide film was then systematically changed by repeatedly cycling up to the forming voltage. At the same time, the resulting in-plane electrostriction stress was determined from high-resolution in situ curvature measurements. For the TiO₂ films considered, compressive in-plane electrostriction stresses up to −240 MPa were measured. This is an order of magnitude higher than previous predictions which neglected the contribution of the electrostriction parameters. Moreover, the measured stress values, their field-dependence and the derived electrostriction parameters are shown to be in agreement with the modified theory.     

Enhanced electrochromic performance of macroporous WO3 films formed by anodic oxidation of DC-sputtered tungsten layers

Self-organized macroporous tungsten trioxide (WO₃) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO₃ films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H₂SO₄, the macroporous WO₃ films show enhanced electrochromic properties with a coloration efficiency of 58 cm² C⁻¹. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.     

Nanometer copper-tin alloy anode material for lithium-ion batteries

Nanometer copper-tin alloy anode materials with amorphous structure were prepared by a reverse microemulsion technique for lithium-ion batteries. It was found that the electrochemical performance of alloy was influenced by its particle size, which was controlled by appropriate surfactant content. The nanometer copper-tin alloy with particle size of 50-60 nm presented the best performance, showing a reversible specific capacity of 300 mA h/g over the full voltage range 0.0-1.2 V and capacity retention of 93.3% at 50 cycles. A great irreversible capacity was caused by the formation of a SEI layer on the surface of nanometer alloy. The contact resistance between nanometer particles resulted in the poor electric conductivity and the match of particle size and conductive agent content had a great impact on the electrochemical performance of the nanometer copper-tin alloy anode.     

Pore diameter control of anodic aluminum oxide with ordered array of nanopores

Highly uniform, self-ordered anodic aluminum oxide (AAO) with an ordered nanoporous array can be effectively formed from industrially pure (99.5%) aluminum sheets through an anodizing program in a mixture solution of sulfuric and oxalic acids. The influences of anodizing variables, such as applied voltage, solution temperature, oxalic acid concentration, agitation rate, and sulfuric acid concentration, on the average pore diameter of AAO were systematically investigated using fractional factorial design (FFD). The applied voltage, and sulfuric acid concentration were found to be the key factors affecting the pore diameter of AAO films in the FFD study. The pore diameter of AAO is regularly increased from ca. 50 to 150 nm when the applied voltage and the concentration of sulfuric acid are gradually increased from 53 to 80 V and from 3.5 to 8 M, respectively. Fine tuning of the pore diameter for AAO films with an ordered, nanoporous, arrayed structure from industrially pure aluminum sheets can be achieved.     

Photoluminescence of hydrothermally epitaxied ZnO films

In this study, epitaxial ZnO films were grown hydrothermally on (1 1 1)-oriented single crystal MgAl₂O₄ substrates at 150 °C from aqueous precursor solutions. It was observed that the film morphology varied with the pH value of the precursor solution, giving pitted films at higher pH and smooth films at lower pH. The photoluminescence spectra of these ZnO films showed a strong near band-edge ultraviolet emission together with deep level emission bands comprised of green and orange-red luminescence. The green band centred around 500 nm was attributed to the presence of Zn vacancies, whereas the orange-red band centred around 650 nm could be related to the presence of oxygen interstitials.     

Synthesis and photophysics of new highly luminescent poly(alkylthiophene) derivatives with pyridine in the backbone

Starting from 2,6-bis-(3-octylthiophene-2yl)-pyridine, two new poly(alkylthiophene) derivatives, POTPyOT and POTPy, containing pyridine in the backbone were prepared from nickel(0)-mediated Stille coupling or by palladium-catalyzed Yamamoto coupling. These polymers exhibited good solubility in common organic solvents, thermal stability up to 400 °C, and facile film formation. They were amorphous and give strong luminescence both in CHCl₃ solution and solid state film. The polymers emitted blue light in solution with photoluminescence (PL) emission maximum at 420-484 nm and green light with PL emission maximum at 500-514 nm in thin films. These polymers showed a reversible redox reaction at potential from 0 to 1.3 V (vs. SCE). Nevertheless, the reduced form of the polymer was very unstable; it decomposed in the presence of oxygen or water. The emission and UV-vis absorption of the polymer were influenced by the solvent polarity, protonation, and acid-base treatment. These may be the results of the stabilization of the polar excited state by solvation and the change of the conformation in polymer backbone. Electroluminescence (EL) was achieved from a single-layer PLED with the configuration of ITO/POTPyOT/Al. The turn-on voltage of the device is 10 V and the λ_max (550 nm) of the EL is voltage independent.     

Effect of ion bombardment and hydrogen pressure during deposition on the optical properties of hydrogenated amorphous carbon thin films

Carbon-based thin films are ideal materials for several state-of-the-art applications, such as protective materials and as active films for organic electronics, medical, optoelectronic devices. In this work, we study in detail the effect of the ion-bombardment and the hydrogen partial pressure during deposition on the optical properties of hydrogenated amorphous carbon (a-C:H) thin films grown onto c-Si substrates by rf magnetron sputtering. The optical properties of the a-C:H films were investigated by phase modulated Spectroscopic Ellipsometry in a wide spectral region from the NIR to the Vis-far UV (0.7-6.5 eV). A dispersion model based on two Tauc-Lorentz oscillators, has been applied for the analysis of the measured < ε(ω)> of the a-C:H films to describe the π-π* and σ-σ* interband electronic transitions, that can describe accurately the optical properties of all amorphous carbons. The applied V_b influences the bombardment of the growing thin films with Ar ions affecting the content of sp² and sp³ hybridized carbon bonds in the films. As it was found, the increase of the applied negative voltage reduces the optical transparency of the a-C:H films. Also, the H incorporation has been found to change only the energy position of the σ-σ* transitions. Finally, from the study of the refractive index n(ω = 0 eV) it has been found that the increase of the ion bombardment during the films deposition is correlated to an increase in the films density.     

Self-ordering of anodic porous alumina formed in organic acid electrolytes

New self-ordering porous alumina films were fabricated in organic acid electrolytes. Highly ordered cell arrangements of porous alumina films were realized in malonic acid at 120 V and tartaric acid at 195 V having 300 nm and 500 nm pore intervals, respectively. Self-organization was achieved at the maximum voltage required to induce high-current-density anodization while preventing burning, i.e., an extremely high-current flow concentrated at local points. The cells of the film grown at a high field must be pressed against each other, so that the self-ordering proceeds with the porous layer growth. When the self-ordering of cell arrangement proceeds, the cells became smaller. To improve the regularity of the cell configuration, a low electrolyte temperature and a relatively high electrolyte concentration were effective for maintaining a high-current-density to prevent burning. Surface flatness was an essential factor for self-ordering, however, the surface oxide film produced by electropolishing an aluminum substrate prevented quick pore growth in the organic acids having a low dissociation constant. It is confirmed that electropolishing followed by alkaline treatment was most appropriate as the pre-treatment in preparing flat surfaces.     

Electrical conductivity and self-temperature-control heating properties of carbon nanotubes filled polyethylene films

Electrical properties of polyethylene and carbon nanotube composite films were investigated, when the composite films were set in heating box or under electric field at constant voltage. The composite films were prepared by gelation/crystallization from dilute solution. The mixture of ultra-high molecular weight polyethylene (UHMWPE) and branched low molecular weight polyethylene (LMWPE) was used as matrix, and multi-walled carbon nanotubes (MWNTs) were used as fillers. The filler content was chosen to be 10 wt% (ca. 5.25 vol%) which is a relatively higher loading than the percolation threshold to ensure to act as heating element in plane heater of composite film. The focus was concentrated on the temperature dependences of electric conductivity by external heating and by exothermic effect concerning self-temperature-control heating properties which were measured for the three kinds of UHMWPE-LMWPE composites with the same content of MWNTs in the composites. When a certain voltage was applied to the composite, the surface temperature of film reaches the equilibrium value within less than 100 s. The maximum surface temperature as the equilibrium state of the resultant composite film can be easily controlled by adjusting the composite ratio represented as UHMWPE/LMWPE. The high efficiency of heating and wide adjustability of stable temperature suggested its good application in high efficient plane heater.     

On the reaction kinetics of Ni with amorphous carbon

The kinetics of the graphitisation of thin films of amorphous carbon (a-C) by supported Ni particles was investigated by in situ transmission electron microscopy. Ni particles were deposited on a-C films at temperatures from 350 to 500 °C, and reactions with the support were recorded at 600 up to 720 °C. The activity was found to strongly depend on temperature. Reactions generally started with encapsulation of Ni particles with a graphite shell, out of which the metal was eventually expelled and spread on the substrate, which was then graphitised. The propagation speed of the reaction front, and the increase with time of its length and of the graphitised area were measured as function of temperature. Through this, an activation energy of 1.8 ± 0.2 eV was determined; such result is significantly comparable to the theoretical estimate of 1.6 eV, reported by other authors.     

Corona discharge from electrospinning jet of poly(ethylene oxide) solution

Corona discharges from electrospinning jets were observed and photographed at the tip of the Taylor cone, and in a cylindrical region around the jet, a few millimeters below the tip. The corona discharge was also faintly visible to a dark adapted eye. At the position at which the cylindrical corona discharge became apparent, typical conditions were a jet diameter of 30 μm, an applied potential of 12 kV, and a calculated radial electric field of 400 kV/cm, The calculated electric field required to create a corona in air around a metal wire of the same diameter, calculated from Peek's empirical formula, was only about 200 kV/cm. The cross sectional shape of some segments of the electrospun fibers had two or three lobes. The lobes often separated, and formed smaller fibers.     

Oxidation characteristics of nanodot and nanobump on TiN thin films by atomic force microscopy

The electrochemical oxidation characteristics of TiN thin films by atomic force microscopy (AFM) was investigated. The TiN films were produced on silicon substrate by atomic layer chemical vapor deposition (ALCVD). The anodization parameters, such as the anodized voltages, the oxidation times, and how they affected the creation and growth of the oxide nanostructures were explored. The results showed that the height of the TiN oxide dots grew as a result of either the anodization time or the anodized voltage being increased. The oxide growth rate was dependent on the anodized voltage and the resulting electric field strength. Furthermore, the oxide growth rate decreased immediately when the electric field strength reached (2-3) × 10⁷ V/cm rapidly decrease to a growth rate of 0.     

Sol–gel-deposition of thin TiO2:Eu thermographic phosphor films

A relatively new promising method for surface temperature measurement is the use of thermographic phosphors. For this application, the temperature-dependent luminescence properties of europium (III)-doped anatase (TiO₂:Eu³⁺) thin films were studied. The films were prepared by the sol–gel method using dip coating. The structures and the morphology of the films were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electron dispersive X-ray spectroscopy (EDX) was used to verify the europium concentration within the films. For using the films as temperature sensors the optical properties are the main concern. Therefore, the emission spectra of the films were measured after ultraviolet laser excitation (355 nm). They indicate that the red characteristic emission (617 nm) of TiO₂:Eu³⁺ due to the ⁵D₀ → ⁷F₂ electric dipole transition is the strongest. The decay time constant of the exponential emission decay under UV excitation with a Nd:YAG laser (355 nm, f = 10 Hz) is strongly temperature dependent in the range from 200 °C up to 400 °C; making it useful for temperature evaluation. The temperature dependence was measured for the emission line at 617 nm; the results demonstrate that anatase doped europium (III) can be used as a thermographic phosphor.     

Effects of thermal annealing on the optical properties of Ar ion irradiated ZnS films

Ar-ion-implantation to a dose of 1×10¹⁷ ions/cm² was performed on cubic ZnS thin films with (111) preferred orientation deposited on fused silica glass substrates by vacuum evaporation. After ion implantation, ZnS films were annealed in flowing argon at different temperatures from 400 to 800 °C. The effects of ion implantation and post-thermal annealing on the structural and optical properties of ZnS films were investigated by X-ray diffraction (XRD), photoluminescence (PL) and optical transmittance measurements. XRD reveals that the diffraction peaks recover at ∼500 °C. The optical transmittances show that the bandgap of ZnS films blueshifts when annealed below 500 °C, and redshifts when annealed above 500 °C. PL results show that the intrinsic defect related emissions decrease with increasing annealing temperature from 400 to 500 °C, and increase with increasing annealing temperature from 500 to 800 °C. The observed PL emissions at 414 and 439 nm are attributed to the transitions of Zn_i→V_Zn and V_S→VBM, respectively.     

Li-intercalation electrochemical/electrochromic properties of vanadium pentoxide films by sol electrophoretic deposition

Thin films of orthorhombic V₂O₅ have been prepared by sol electrophoretic deposition (EPD) followed by post-treatment at 500 °C. Their electrochemical and optical performances have been investigated for possible applications in electrochemical/electrochromic devices. Li⁺-intercalation properties of the films have been explored in two voltage ranges: 0.4 to −1.1 V and 0.4 to −1.6 V versus Ag/Ag⁺, respectively. High capacities of over 300 mAh/g are acquired in the wider voltage range at a current density of 50 μA/cm² and moderate capacities of 140 and 110 mAh/g are obtained in the narrower voltage range at a current density of 25 and 50 μA/cm², respectively. Electrochemical measurements have shown that the films demonstrate good cyclability in both voltage ranges. X-ray diffraction, scanning electron microscopy and optical spectra have been used to examine the changes in crystallinity, microstructure, morphology and transmittance of the films during cycling. Films cycled to a deeper voltage of −1.6 V versus Ag/Ag⁺ deliver higher capacity with appreciable morphological change, while films cycled in the narrower voltage range show moderate capacity and maintain the morphology, optical responses and crystalline structure. Voltage range can be optimized in between to acquire both high capacity and stability in structure, electrochemical and optical properties. High Li⁺-intercalation capacity and good cyclic stability are attributed to the porous structure of V₂O₅ films prepared by EPD.     

Diamond overgrown InAlN/GaN HEMT

In this work the technology and characterization of nanocrystalline diamond (NCD) films directly grown on InAlN/GaN HEMTs is presented. Optimization of GaN based HEMT process steps including metallization stacks is discussed. A fully processed InAlN/GaN HEMT structure with 7 nm barrier has been overgrown in a temperature range of 750 °C to 800 °C with a 500 nm thick nanocrystalline diamond film in a Hot Filament CVD system. First results of semi-enhancement mode of DC and RF HEMT operation are reported. The grown NCD films were characterized by SEM, TEM, and Raman spectroscopy. Although no direct thermal conductivity measurements are conducted yet; the performed experiments shows the compatibility of growing high quality NCD films, several microns thick, on InAlN/GaN HEMTs as a potential material for heat extraction purposes.     

DC-field-induced synthesis of ZnO nanowhiskers in water-in-oil microemulsions

ZnO nanowhiskers were successfully fabricated using DC-field induced water-in-oil microemulsions method. Phase structure, morphology and microstructure of the product were investigated by X-ray diffraction and transmission electron microscopy. Parameters in preparation process such as electric field intensity and surfactant were discussed and the product formation mechanism was studied. XRD and TEM results showed that the obtained ZnO particle was hexagonal wurtzite-type with 1-3 nm in diameter and 20-70 nm in length, and morphology of the particles was shown to be correlated not only with the electric field intensity but also with the surfactant. There was a threshold when the electric field intensity was 80 V/mm. The morphology of the particles was basically spherical before the threshold, while L/D increased with the raise of electric field intensity. ZnO nanowhiskers were obtained under mixed surfactants but spherical particles were got with a single surfactant.