Ellipsometric study of anodic oxide films formed on niobium surfaces

Anodic oxide films formed potentiostatically on niobium surfaces, from open circuit potential (OCP) to 10 V, were studied by performing in situ and ex situ ellipsometric measurements. The kinetics of the film thickness growth in 1 M H₂SO₄ and complex indices of refraction of these films were determined. A strong influence of the surface preparation conditions on the complex refractive indices of the metal substrate and anodic oxide films was shown. By steady-state measurements at OCP, a small thickening of the natural air-formed oxide film with chemical composition Nb₂O₅ in 1 M H₂SO₄ solution was detected. With cathodic pre-treatment, only partial reduction and small thinning of the natural air-formed oxide film was possible. The thicknesses of the natural air-formed oxide films on fine mechanically polished and electropolished Nb surfaces were determined. The build up of the natural air-formed oxide film, at ex situ conditions, on the already formed anodic oxide films was confirmed. It was shown that electropolishing gives more similar optical surface properties to the bare metal than the fine mechanical polishing. Electronic Publication     

Nitridation of niobium oxide films by rapid thermal processing

The possibility of forming niobium oxynitride through the nitridation of niobium oxide films in molecular nitrogen by rapid thermal processing (RTP) was investigated. Niobium films 200 and 500 nm thick were deposited via sputtering onto Si(100) wafers covered with a thermally grown SiO₂ layer 100 nm thick. These as-deposited films exhibited distinct texture effects. They were processed in two steps using an RTP system. The as-deposited niobium films were first oxidized under an oxygen atmosphere at 450 °C for various periods of time and subsequently nitridated under a nitrogen atmosphere at temperatures ranging from 600 to 1000 °C for 1 min. Investigations of the oxidized films showed that samples where the start of niobium pentoxide formation was detected at the surface and the film bulk still consisted of a substoichiometric NbO_x phase exhibited distinctly lower surface roughness and microcrack densities than samples where complete oxidation of the film to Nb₂O₅ had occurred. The niobium oxide phases formed at the Nb/substrate interface also showed distinct texture. Zones of niobium oxide phases like NbO and NbO₂, which did not exist in the initial oxidized films, were formed during the nitridation. This is attributed to a “snow-plough effect” produced by the diffusion of nitrogen into the film, which pushes the oxygen deeper into the film bulk. These oxide phases, in particular the NbO₂ zone, act as barriers to the in-diffusion of nitrogen and also inhibit the outdiffusion of oxygen from the SiO₂ substrate layer. Nitridation of the partially oxidized niobium films in molecular nitrogen leads to the formation of various niobium oxide and nitride phases, but no indication of niobium oxynitride formation was found. Figure Schematic representation of the phase distribution in 200 nm Nb film on SiO₂/Si substrate after two steps annealing using an RTP system. The plot below represents the SIMS depth profiles of the nitridated sample with the phase assignment     

UV-Vis and Raman Spectral Analysis of Polyaniline/Gold Thin Films as a Function of Applied Potential

Polyaniline and polyaniline/gold films were prepared by potentiodynamic oxidation of aniline in 1 M H₂SO₄ aqueous solution, and their electrochromic properties were investigated by UV-Vis and Raman spectroscopy. Both tetrachloroaurate and gold nanoparticles were used to deposit gold onto or inside the polyaniline film based on the deposition technique used. Polyaniline films showed multiple color changes (blue to green to yellow) depending on the electrochemical reactions in the potential range ?0.2 to 0.8 V vs. Ag/AgCl. The color of polyaniline films changed from transparent green to yellow at the anodic peak around 0.2 V and gradually changed from green to dark blue at potentials higher than 0.5 V. The deterioration of electrochromic properties is caused by hydrolysis of the diimine structure formed by oxidation at 0.8 V. Furthermore, the polyaniline films showed enhanced Raman characteristics (due to SERS) depending on the treatments with gold and the potentials applied to the films to control the oxidation state.     

Novel sulfur-doped niobium pentoxide nanoparticles: fabrication, characterization, visible light sensitization and redox charge transfer study

Novel sulfur-modified niobium(V) oxide nanoparticles (SNON) that firstly exhibited good visible light sensitization were fabricated by a modified sol–gel technique using a very stable sol containing niobium(V) chloride, oxalic acid, isopropanol as chelating agent and thiourea as sulfur source. The resulting S-doped Nb₂O₅ nanomaterials were characterized by cyclic voltammetry (CV), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDAX), scanning electron microscope (SEM), ultra-violet diffuse reflectance (UV-DRS) and thermogravimetry thermal Analysis (TG-DTA). As against the response of unmodified niobium(V) oxide nanoparticles (UNON), the doped samples show different electrochemical response indicating an induced charge transfer across the niobium pentoxide/solution interface, thus forming two anodic peaks and a cathodic peak. This important observation was confirmed by UV-DRS in terms of band bending due to sulfur doping. Upon sulfur-modification, the absorption edge extends into the visible light region. The SEM observation shows that the SNPN existed in the mode of polycrystalline structure and the average grain size 63 nm. The EDAX analysis of undoped Nb₂O₅ and sulfur doped Nb₂O₅ shows the Nb₂O₅ (98%) and S (2%) content of nanopowder. These SNON nanoparticles are expected to be suitable candidates as visible light niobium(V) oxide nanoparticles sensitization.     

Characterization of niobium(v) oxide received from different sources

The characterization of three commercial powders of niobium(V) oxide received from two producers was made. The thermal behavior of Nb₂O₅ up to melting point and its microstructure were studied using X-ray powder diffraction, thermoanalytical methods (DSC/TG), infrared spectroscopy (IR) and scanning microscopy. Analysis of the obtained results revealed that the starting structure of niobium(V) oxide and its thermal behavior depend on the origin of niobia. Depending on the origin of the powder and of its thermal treatment, three polymorphs of Nb₂O₅ can be observed. Sintering of powders above 1200 °C results in the formation of single phase, H-Nb₂O₅.     

Comments on the processing of the niobium component for chemical solution derived niobium oxide-based thin-films

The impact of chemical precursor modification on the electronic properties of chemical solution deposition derived niobium oxide thin-films has been evaluated. It has been found that the application of certain chemical modifications is mandatory in order to obtain electrically insulating thin-films at low processing temperatures. It is emphasized that the devised optimal way of processing for the niobium component is widely contrary to the solution based processing of potassium sodium niobate films reported so far. Regarding the physical nature of the observed instabilities, the phase evolution of solution processed niobium oxide films has been studied. It has been detected that the organic fraction in the precursor solution is stable up to high temperatures and as a result, the low temperature crystalline TT-phase of niobium oxide is preserved up to unusually high processing temperatures. The inherent structural distortion of the unit cells may present a new defect mechanism that has to be further investigated regarding the inferior ferroelectric properties of chemical solution derived potassium sodium niobate thin-films, which are often observed.     

Fabrication and characterization of three-dimensionally ordered macroporous niobium oxide

Three-dimensionally ordered macroporous (3-DOM) niobium oxide was fabricated by aqueous organic gel method through the interstitial spaces between polystyrene spheres assembled on glass substrates. Freshly precipitated hydrous niobium oxide (Nb₂O₅·nH₂O), which was prepared starting from Nb₂O₅, was used in combination with citric acid in an aqueous solution and then was transferred as a niobium source to synthesize 3-DOM Nb₂O₅. The morphologies of porous Nb₂O₅ were characterized by scanning electron microscope (SEM). The thermal decomposition and phase composition of 3-DOM Nb₂O₅ were investigated by Fourier transform infrared spectroscopy (FT-IR), Thermogravimetric–differential thermal analysis (TG–DTA), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).     

The preparation of new oxoniobium(V) complexes from hydrated Niobium(V) Oxide: the crystal and molecular structure of Oxotris(2-pyridinolato-<Emphasis Type="Italic">N</Emphasis>-oxide)niobium(V)

Three oxoniobium(V) complexes ONbL₃ with HL = tropolone (1), 2-pyridinol-N-oxide (2) or, 3-hydroxy-1,2-dimethyl-4(1H)-pyridone (3) are obtained in good yield by one step reactions from commercially available hydrated niobium(V) oxide in aqueous media. The products are characterized by elemental analysis, FT-IR spectroscopy, NMR spectroscopy (¹H- and ¹³C-) and thermogravimetry. The crystal structure of oxotris(2-pyridinolato-N-oxide)niobium(V) is determined by single crystal X-ray diffraction, showing discrete molecules with pentagonal bipyramidal coordinated niobium. The ¹H-NMR spectra of CDCl₃ solutions indicate a fluxional behaviour for the three complexes.     

Lithium electrochromism of atmospheric pressure plasma jet-synthesized NiO x C y thin films

Reversible lithium intercalation and deintercalation behavior of atmospheric pressure plasma jet (APPJ)-synthesized organonickel oxide (NiO _x C _y ) thin films under various substrate distances is testified in an electrolyte (1?M LiClO₄–propylene carbonate solution) at low driving voltages from ?0.5 to 1.5?V. Fast responses of 2?s bleaching at ?0.5?V and 6?s coloration at +1.5?V are accomplished for the nano-porous NiO _x C _y thin films. This study reveals that a rapid synthesis of electrochromic NiO _x C _y thin films in a single process via APPJ by 21?s is investigated. This study presents a noteworthy electrochromic performance in a light modulation with up to 43% of transmittance variation and a coloration efficiency of 36.3?cm²/C at a wavelength of 830?nm after 200?cycles of cyclic voltammetry measurements.     

Complex formation of polymeric niobium and tantalum pentafluorides in non-aqueous solvents

¹⁹F NMR and i.r. spectroscopy were employed to study complex formation of niobium and tantalum pentafluorides with triphenylphosphine oxide, ethyl diphenylphosphinate and S-ethyl diphenylthiophosphinate in methylene chloride and in acetonitrile. In methylene chloride solution MF₅L, M₂F_IOL, MF₄L₂⁺ and M₂F_II^? complexes were found (M=Nb, Ta;L- phosphoryl-containing Ligand). I.r. frequencies are assigned. Solvent properties (electric conductivity and donor capacity) affect the relative stability of complexes. The dependence of ¹⁹F NMR parameters on the donor capacity of the ligands is discussed.     

Dielectric properties of Al–Si composite oxide films formed on electropolished and DC-etched aluminum by electrophoretic sol-gel coating and anodizing

Highly pure aluminum specimens (99.99%) after electropolishing and DC-etching were covered with SiO₂ films by electrophoretic sol-gel coating and were anodized in neutral boric acid/borate solutions. Time-variations in cell voltage during electrophoretic sol-gel coating and in anode potential during anodizing were monitored. Structure and dielectric properties of the anodic oxide films were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX), and electrochemical impedance spectroscopy (EIS). It was found that electrophoretic sol-gel coating forms uniform SiO₂ films on the surface of both electropolished and DC-etched specimens. Anodizing of specimens after electrophoretic coating lead to the formation of anodic oxide films consisting of two layers: an inner alumina layer and an outer Al–Si composite oxide layer. The anodic oxide films formed, thus, had slightly higher capacitances than those formed on aluminum without any coating. Higher heating temperatures after electrophoretic deposition caused the increase in capacitance of anodic oxide films more effectively. Anodizing in a boric acid solution after SiO₂ coating on DC-etched foil allowed the anode potential to reach a value higher than 1,000 V, resulting in 39% higher capacitances than those on specimens without SiO₂ film. Dedicated to Professor Su-Il Pyun on the occasion of his 65th birthday.     

Separation of trace concentrations of tantalum from niobium and some other heavy metal ions by extraction with N-oxide of trioctylamine

The distribution of tantalum(V) between 0.1M trioctylamine oxide dissolved in xylene and sulphuric acid solutions has been studied. On the basis of results on the distribution, it is concluded that at sulphuric acid concentration 0.5M, tantalum is probably extracted by a solvate mechanism as the complex Ta(OH) (SO₄)₂·3TOAO. It has also been shown that tantalum can be quantitatively separated from niobium, uranium, thorium and rare earth elements by extraction with N-oxide of trioctylamine from 0.5M sulphuric acid solution.     

Electrochemical and Electrochromic Properties of Ni Oxide Thin Films Prepared by a Sol–Gel Method

Nickel oxide thin films, which are well known anodic coloration materials that are used in electrochromic devices, were prepared by a sol–gel method, and their electrochemical and electrochromic properties were investigated. The sol was prepared from Ni(OH)₂ powder with an average size of 7 nm, in a mixture of ethylene glycol and absolute ethanol. The films were coated on an ITO substrate using the powder, dispersed in the solution. When additive materials, acetyl acetone and glycerol, were added to the sol its hardness and adhesion properties were improved. The optimized thin film formed an amorphous, porous structure, and showed a large current density during continuous potential and pulse potential cycling. The film also was transparent and had a high coloration efficiency (33.5 cm²/C) and a rapid response time (1.0–2.5 s) during the coloring/bleaching process.     

Extraction and spectrophotometric determination of niobium by tetraphenylarsonium and phosphonium chloride from a hydrochloric acid solution

The extraction of niobium(V) in the form of a chloro complex has been studied. Radiometrical and spectrophotometrical studies show that niobium(V) is extracted practically completely from a solution containing more than 9 mol dm^?3 chloride in the range of 2–5 M hydrogen ion concentration by chloroform solutions of tetraphenylarsonium (TPA) and tetraphenylphosphonium (TPP) chloride and that niobium is not extracted at chloride concentrations less than 6 mol dm^?3. The mechanism of extraction is based on the formation of the ion-associated compounds that form between the onium cation and the oxotetra-chloroniobate(V) anion. The extracted complexes in chloroform have a maximum absorbance at 282 nm (TPA) and 285 nm (TPP); they obey Beer's law in the range of 1–10 μg Nb ml^?1, and are stable for at least 24 hr. The molar absorptivity of the method is 1.33 × 10⁴ dm³ mol^?1cm^?1. The composition of the extracted species [(C₆H₅)₄X] [NbOCl₄] where X = As or P was determined spectrophotometrically, radiometrically, and by characterization of the crystalline compounds isolated.     

Photoelectrochemistry of indium hexacyanoferrate–titania composite films

The voltammetric and electrochromic behavior of two types of indium(III) hexacyanoferrate(II/III) (InHCF) films, potentiodynamically grown either on polycrystalline Au or on tin-doped indium oxide (ITO) support electrodes, are described. A new spectral feature was seen at ca. 475 nm for the InHCF films grown on Au under extended potential window (EPW) conditions, in addition to the dominant 420 nm feature described by previous authors. The 420 nm band is the sole electrochromic feature in films grown under restricted potential window (RPW) conditions. The InHCF films were also grown in the presence of TiO₂ particles in the deposition bath. The resultant InHCF–TiO₂ composite films showed distinctly different photoelectrochemical responses for the EPW and the RPW counterparts. X-ray phoelectron spectroscopy data showed a higher TiO₂ particle uptake for the EPW films relative to their RPW counterparts, under otherwise identical growth conditions. A second film configuration built up by InHCF derivatization of a pre-formed In–TiO₂ film, yielded decidedly inferior photoresponses. Mechanistic reasons for this are presented as is evidence for the dominance of two distinct forms of InHCF under the EPW growth conditions.     

Preparation of alkaline solutions of niobium(V)

Alkaline niobium(V) solutions containing up to 190 g l⁻¹ of niobium oxide were prepared by sintering niobium(V) oxide with potassium carbonate and following leaching of the sinters with water.     

Oxygen addition effects on electrochromic properties of PECVD-synthesized WO x C y films for flexible electrochromic devices

An investigation was conducted into the electrochromic properties of organotungsten oxide WO _x C _y films synthesized onto 60 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates using low temperature, plasma-enhanced chemical vapor deposition (PECVD) at varying oxygen concentrations. The PECVD-synthesized WO _x C _y films were proven to offer remarkable electrochromic performance. Cyclic voltammetry switching measurements revealed that only low driving voltages from −1 to 1 V are needed to provide reversible Li⁺ ion intercalation and de-intercalation in a 0.1 M LiClO₄–PC electrolyte. Light modulation with transmittance variation of up to 72.9% and coloration efficiency of 62.5 cm²/C at a wavelength of 650 nm was obtained.     

Oxidizing valve metals: effect of electronic properties of the oxide films

Photocurrents emerging during the formation of anodic oxide films (AOF) on such valve metals as W, Ti, Zr, Nb, Ta are measured during an increase (direct run) and a decrease (reverse run of voltammetric curves) in the anodic potential. Capacitances of AOF formed at certain potentials are measured at potentials below the AOF formation potential. Effect of semiconductor properties on the AOF growth is considered through the formation of a Schottky barrier at the oxide/electrolyte interface. Calculated thicknesses of AOF and the depleted layer are compared. The donor-concentration drop in AOF with the distance from the metal/oxide interface is a condition for the growth of thick semiconductor oxide films. The measured potential dependence of the semiconductor-film capacitance is used to plot the donor concentration drop as a function of the distance from the Nb₂O₅/Nb interface in the oxide layer on a niobium electrode. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

Modification of niobium surfaces using plasma electrolytic oxidation in silicate solutions

Herein, a study of the plasma electrolytic oxidation (PEO) of niobium in an anodising bath composed of potassium silicate (K₂SiO₃) and potassium hydroxide (KOH) is reported. The effects of the K₂SiO₃ concentration in the bath and the process voltage on the characteristics of the obtained oxide layers were assessed. Compact, barrier-type oxide layers were obtained when the process voltage did not exceed the breakdown potential of the oxide layer. When this threshold was breached, the morphology of the oxide layer changed markedly, which is typical of PEO. A significant amount of silicon, in the form of amorphous silica, was incorporated into the oxide coatings under these conditions compared with the amount obtained with conventional anodising. This surface modification technique led to an improvement in the corrosion resistance of niobium in Ringer’s solution, regardless of the imposed process conditions.     

Synthesis and catalytic properties of niobium indenyl peroxo complexes

Synthesis of four niobium sandwich peroxo complexes containing fragments of substituted indenes was performed and their structure was proved by NMR spectroscopy and ESI-MS mass spectrometry. Catalytic activity of the complexes in the oxidation of sulfides with hydrogen peroxide was studied, and a high selectivity in the oxidation of sulfides to sulfoxides and sulfones of the sandwich peroxo complexes was found.