0000000000206136
AUTHOR
F. Di Franco
Fabrication of Bismuth Absorber Arrays for NTD-Ge Hard X-ray Microcalorimeters
The high-spectral-resolution detection of hard X-rays (E > 20 keV) is a challenging and nearly unexplored area in space astrophysics. Traditionally hard X-ray detectors present moderate spectral resolutions, although few tens of eV one could open new frontiers in the study of nuclear processes and high-temperature plasma dynamics in energetic processes. This can be achieved by using cryogenic microcalorimeters. Within a research activity aimed at developing arrays of neutron transmutation-doped germanium (NTD-Ge) microcalorimeters for the high-spectral-resolution detection (about 50 eV@60 keV) of hard X-rays (20 keV < E<100 keV), we developed an electroplating process to fabricate …
Light induced electropolymerization of poly(3,4-ethylenedioxythiophene) on niobium oxide
Abstract The photoelectrochemical polymerization of poly(3,4-ethylenedioxythiophene), PEDOT, was successfully realized on anodic film grown to 50 V on magnetron sputtered niobium. Photocurrent Spectroscopy was employed to study the optical properties of Nb/Nb 2 O 5 /PEDOT/electrolyte interface in a large range of potential, and to get an estimate of the band gap and flat band potential of both the oxide and the polymer. Scanning Electron Microscopy was used to study the morphology of PEDOT. Both the optical and morphological features of the photoelectrochemically grown polymer were compared with those showed by PEDOT electropolymerized on gold conducting substrate.
Electronic properties and corrosion resistance of passive films on austenitic and duplex stainless steels
Abstract Passive films were grown at constant potential in acidic (pH∼2) and alkaline (pH∼13) solutions on chromium, AISI 304L, AISI 316L and Duplex stainless steels. Passive films on chromium grow following a high field mechanism considering the presence of dissolution phenomena. According to the photoelectrochemical characterization, passive films on Cr have a bandgap of 3.4 eV when formed in acidic solution, and of 2.4 eV when formed in alkaline solution due to the formation of Cr(OH)3. These films result to be poorly stable against anodic dissolution due to a very anodic flat band potential. Conversely, impedance and photoelectrochemical measurements proved that passive films on stainle…
Influence of anodizing surface treatment on the aging behavior in salt-fog environment of aluminum alloy 5083 to fiber reinforced composites adhesive joints
The present work aims to evaluate how an innovative and eco-friendly anodizing process with tartaric-sulfuric acid (TSA) bath and a pore widening in an aqueous solution of NaOH 0.1 M can improve the durability in marine environment of co-cured adhesive joints between an aluminum alloy (AA 5083) and fiber (i.e., glass or basalt)-reinforced composite substrates. The aging was carried out by exposing samples to salt-fog spray conditions (5 wt.% NaCl) for 30, 60 and 90 days in a climate chamber, in accordance with ASTM B117. In order to get further insights on the aging behaviour of bonded joints, neat matrix was also exposed to the same environment for 60 days. Quasi-static mechanical tests an…
Electronic Properties of Thermal Oxides on Ti and Their Influence on Impedance and Photoelectrochemical Behavior of TiO2 Nanotubes
Thermal oxidation of titaniumwas carried out at 350◦C, 450◦C, and 550◦C for 2 h or 12 h.X-rayDiffraction and Raman Spectroscopy suggest that the thermal oxides are scarcely crystallinewhen the annealing temperature is low, while both anatase and rutile are present for high annealing temperature and time. Photoelectrochemical measurements allowed estimation of a bandgap decreasing from 3.35 eV to 3.15 eV with increasing annealing temperature. The impedance spectra confirmed the formation of n-type semiconductors, with an impedance strongly decreasing on going from a reverse bias toward a forward bias regime. TiO2 nanotubes grown by anodizing Ti in NH4F and water containing ethylene glycol so…
Phosphomolybdic acid and mixed phosphotungstic/phosphomolybdic acid chitosan membranes as polymer electrolyte for H2/O2 fuel cells
Abstract Flat, free-standing phosphomolybdic acid and mixed phosphotungstic/phosphomolybdic acid chitosan membranes were prepared by in-situ ionotropic gelation process at room temperature on porous alumina support firstly impregnated by heteropolyacid. Scanning electron microscopy revealed the formation of compact and homogenous polymeric membranes, whose thickness resulted to be dependent on reticulation time, and almost independent on the employed heteropolyacid nature and concentration. X-ray diffraction and Fourier transform infrared spectroscopy evidenced the formation of crystalline membranes without appreciable concentration of unprotonated NH 2 groups and heteropolyacid ions with p…
Effect of E. coli biofilm formation and removal on passive films on AISI 316L during fermentation processes
Abstract 316L coupons were sanitized in hot water vapour inducing iron enrichment in passive films. Coupons were then immersed in a pilot fed-batch fermenter in presence of E. coli. Sanitization causes iron enrichment in passive films. Fermentation causes the growth of biofilm on the SS, constituted by bacteria embedded in an extracellular polymeric substance. During fermentation SS open circuit potential is very negative due to low oxygen concentration on its surface, while the chelating action of siderophores induces chromium enrichment in the passive film. Disinfection in NaClO for 30 min allows removal of biofilm and formation of a protective passive film.
Role of Molybdenum on the Electronic Properties of Passive Films on Stainless Steels
Potentiostatic polarization of different stainless steel grades with a mirror surface finishing was performed in order to investigate the role of Mo on stainless steels corrosion behaviour. In the attempt to gain more insight into transpassive dissolution mechanism, passive films were grown in neutral aqueous solution (pH ∼ 7) at different polarizing potentials ranging from passive to transpassive conditions. According to the photoelectrochemical characterization, Cr dissolution occurs even at low polarizing potentials in the case of AISI 304L, while higher band gap values were obtained for passive films grown on austenitic 316L and duplex SSs. Capacitance measurements suggest that the flat…
Semiconducting properties of passive films and corrosion layers on weathering steel
Abstract Anodic films were grown on Weathering Steel by potentiostatic polarization in slightly alkaline solution. The photoelectrochemical results reveal that they are n-type iron oxide with Eg = 2.0 eV. Rust layer grown by atmospheric corrosion are n-type semiconductors with a band gap higher than that estimated for the anodic film attributed to the formation of γ-lepidocrocite. The electrochemical impedance spectra allow to evidence that rust layers have a higher conductivity with respect to anodic films due to the presence of highly doped iron oxide layers. The use of Mott-Schottky theory to model the dependence of oxide capacitance as function of potential is critically discussed.
Erroneous p-type assignment by Hall effect measurements in annealed ZnO films grown on InP substrate
We report on incorrect carrier type identification achieved by Hall effect measurements performed on ZnO films grown by pulsed laser deposition on InP substrates and subsequently annealed for 1 h at 600 C in air. While Hall measurements, after post-growth annealing, reveal a change in the electrical properties of the films, from n-type to p-type, both photocurrent-based and standard C V measurements performed on the same samples show no change in the native n-type doping of the ZnO films. A possible interpretation of the two results is reported. In particular, p-type conductivity observed by Hall effect may be ascribed to a highly conductive thin layer formed during the annealing process at…
Characterization of the Solid State Properties of Anodic Oxides on Magnetron Sputtered Ta, Nb and Ta-Nb Alloys
Tantalum oxide, niobium oxide and Ta-Nb containing mixed oxides were grown by anodizing sputter-deposited Ta, Nb and Ta-Nb alloys of different compositions. A photoelectrochemical investigation was performed in order to estimate the band gap and the flat band potential of the oxides as a function of their composition. The band gap of the investigated Ta-Nb containing mixed oxides changed monotonically between those estimated for Ta2O5 (4.1 eV) and Nb2O5 (3.4 eV) and in agreement with a proposed correlation between the Band gap of an oxide and the difference of electronegativity of the oxide constituents. From the differential capacitance curves recorded in a wide range of electrode potentia…
Photoelectrochemical and XPS characterisation of oxide layers on 316L stainless steel grown in high-temperature water
Passive films on AISI 316L stainless steel were grown by exposure in high temperature (300 °C and 150 bar) water. X-ray photoelectron spectroscopy was employed to study their composition as a function of immersion time. A photoelectrochemical investigation, supported by electrochemical and impedance measurements, allowed to get information on the solid-state properties of the investigated layers. The experimental results suggest the formation of a stratified layer with an outer iron-rich layer and an inner Cr-rich oxide layer, whose relative thickness and composition are dependent on the immersion time.
Electrochemical fabrication of metal/oxide/conducting polymer junction
After discovery of conducting polymers and the possibility to modify their electrical properties from insulating to metallic like behavior by doping and a careful choice of the processing conditions, a large amount of research effort has been devoted to the theoretical understanding of their solid state properties as well as to exploit the possible application of conducting polymers in many technological fields including large area organic electronics, polymer photovoltaic cell, and sensors. 1-4 Organic thin film transistors appear very promising devices for the development of low cost, flexible, and disposable plastic electronics. In order to reduce the operating voltage it has been sugges…
Photocurrent spectroscopy in passivity studies
The aim of this article is to present photocurrent spectroscopy as useful in situ technique for the physicochemical characterization of passive films and corrosion layers. The response of (both amorphous and crystalline) semiconductor/electrolyte junction under irradiation is treated and discussed in order to get information about solid-state properties such as band gap and flat band potential. The possibility to use Photocurrent Spectroscopy (PCS), in a quantitative way, to get information on the composition of corrosion layers is discussed through a semiempirical correlation between the band gap of the oxides (or hydroxides) and the difference of electronegativity of their constituents. F…
Improvement in the performance of low temperature H2-O2 fuel cell with chitosanephosphotungstic acid composite membranes
Abstract Free-standing chitosan/phosphotungstic acid polyelectrolyte membranes, prepared by ionotropic gelation on alumina porous supports, were employed as proton conductor in low temperature H 2 –O 2 fuel cell. A drying step on glass substrate was introduced in the fabrication procedure to reduce shrinkage and consequent corrugation. Membranes were tested with electrodes prepared according to different procedures and with two different Pt loadings, namely 0.5 and 1 mg cm −2 . Both the investigated kinds of electrodes allowed to get very promising power peaks of 550 mW cm −2 in spite of the different Pt content. The polarization curves and the electrochemical impedance spectra suggest that…
Photoelectrochemical Evidence of Cu2O/TiO2 Nanotubes Hetero-Junctions formation and their Physicochemical Characterization
Cu2O/TiO2 nanotubes heterojunctions were fabricated by electrochemical deposition of cuprous oxide on TiO2 nanotubes arrays grown by anodizing. X-ray diffraction and Raman Spectroscopy analysis allows for identification of Cu2O, whose morphological features were studied by Scanning Electron Microscopy as a function of the charge circulated during the electrodeposition step. Photoelectrochemical measurements in aqueous solutions evidenced a red shift of the light absorption threshold of TiO2 nanotubes due to the presence of cuprous oxide even for very low circulated charges, while electrochemical impedance measurements proved a significant reduction of the electrode impedance due the presenc…
Photoelectrochemical characterization of amorphous anodic films on Ti-6at.%Si
Abstract The solid state properties of anodic films grown galvanostatically on sputtering-deposited Ti–6at.%Si alloys were studied as a function of the formation voltage (5–40 V). From the photocurrent spectra a band gap of ∼3.4 eV was estimated for all the investigated thicknesses, which is almost coincident with the value measured for amorphous TiO 2 . The photocharacteristics allowed to estimate the flat band potential of the films, which resulted to be more anodic for thicker layers and allowed to evidence a change from n-type semiconducting material to insulator by increasing the formation voltage. A dielectric constant of ∼31 was estimated by differential capacitance measurements. The…
Photoelectrochemical monitoring of rouging and de-rouging on AISI 316L
Electrochemical conditions for inducing rouging on surface of AISI 316L in quasi neutral aqueous solution are studied. Potentiostatic polarization at 0.6 V vs. SSC at pH ∼ 7 allowed growth of colourless passive films with a band gap slightly lower than that estimated for the oxide grown on the SS surface by air exposure due to chromium dissolution. Under stronger anodic polarization (UE = 1.5 V vs. SSC) coloured passive films are formed, mainly constituted by iron oxide according to their band gap (Eg = 2.0 eV). Etching in citric acid at 60 °C results to be effective in removing rouging.
Resistive switching behaviour in ZnO and VO 2 memristors grown by pulsed laser deposition
The resistive switching behaviour observed in microscale memristors based on laser ablated ZnO and VO 2 is reported. A comparison between the two materials is reported against an active device size. The results show that devices up to 300 × 300 μm 2 exhibit a memristive behaviour regardless of the device size, and 100 × 100 μm 2 ZnO-based memristors have the best resistance off/on ratio.
Effect of NaClO disinfection/cleaning on passive films on AISI 316L
Abstract 316 L stainless steel samples were passivated in NaClO containing solutions in order to simulate disinfection processes. Passive films were grown at the open circuit potential by immersion in NaClO aqueous solutions at different concentrations and temperature in order to understand how exposure to aggressive environments could affect subsequent corrosion resistance of SSs. In the attempt to study the passive film growth mechanism, in-situ Open Circuit Potential measurements were performed in the same growth solutions. Photoelectrochemical and impedance investigation of passive films was carried out in order to link their solid state properties with their corrosion behaviour.
Anodization and anodic oxides
Anodizing is a low-temperature, low-cost electrochemical process allowing for the growth, on the surface of valve metals and valve metal alloys, of anodic oxides of tunable composition and properties. This article is an overview on theoretical aspects concerning the general aspects of the kinetics of growth of barrier and porous anodic oxides and some of their present and possibly future technological applications of anodic oxides. The first part of the article is devoted to anodic oxide growth models, from Guntherschulze and Betz work (in 1934) to the more recent results on barrier and porous oxide films. The second part is focused on industrial processes to fabricate anodic oxides and the…
The Effect of Electronic Properties of Anodized and Hard Anodized Ti and Ti6Al4V on Their Reactivity in Simulated Body Fluid
The electronic properties of barrier and porous layers on Ti and Ti6Al4V were studied. Barrier anodic oxides grown to 40 V on Ti and on Ti6Al4V are both n-type semiconductors with a band gap of 3.3 eV and 3.4 eV respectively, in agreement with the formation of amorphous TiO2. Anodizing to 200 V at 20 mA cm−2 in calcium acetate and β-glycerol phosphate disodium pentahydrate leads to the formation of Ca and P containing porous films with a photoelectrochemical behaviour dependent on the metallic substrate. A band gap of 3.2 eV and the flat band potential of −0.5 V vs Ag/AgCl were measured for the porous oxide on Ti, while optical transitions at 2.15 eV and a significantly more positive flat b…
Photoelectrochemical evidence of nitrogen incorporation during anodizing sputtering--deposited Al-Ta alloys.
Anodic films were grown to 20 V on sputtering-deposited Al–Ta alloys in ammonium biborate and borate buffer solutions. According to glow discharge optical emission spectroscopy, anodizing in ammonium containing solution leads to the formation of N containing anodic layers. Impedance measurements did not evidence significant differences between the dielectric properties of the anodic films as a function of the anodizing electrolyte. Photoelectrochemical investigation allowed evidencing that N incorporation induces a red-shift in the light absorption threshold of the films due to the formation of allowed localized states inside their mobility gap. The estimated Fowler threshold for the intern…
Resistive switching in microscale anodic titanium dioxide-based memristors
Licence CC BY-NC-ND The potentiality of anodic TiO2 as an oxide material for the realization of resistive switching memory cells has been explored in this paper. Cu/anodic-TiO2/Ti memristors of different sizes, ranging from 1 × 1 μm2 to 10 × 10 μm2 have been fabricated and characterized. The oxide films were grown by anodizing Ti films, using three different process conditions. Measured IV curves have shown similar asymmetric bipolar hysteresis behaviors in all the tested devices, with a gradual switching from the high resistance state to the low resistance state and vice versa, and a R_OFF/R_ON ratio of 80 for the thickest oxide film devices.
The Amorphous Semiconductor Schottky Barrier Approach to Study the Electronic Properties of Anodic Films on Ti
A detailed study of the electronic properties of thin (>20 nm) anodic TiO2 potentiostatically grown on titanium in two different solutions is presented. The results show that the nature of the anodizing solution affects the electronic properties of the anodic film and, more specifically, the density of electronic states (DOS) distribution. Different DOS were derived from the experimental data analyzed according to the theory of amorphous semiconductor (a-SC) Schottky barrier. It is shown that the usual non-linear and frequency dependent Mott-Schottky plots are in agreement with expected theoretical behavior of a-SC Schottky barrier.
Effects of anodizing surface treatment on the mechanical strength of aluminum alloy 5083 to fibre reinforced composites adhesive joints
Abstract In this study, the anodizing process based on the use of tartaric sulfuric acid solution (TSA) was carried out on metal substrate to evaluate for the first time its effect on the adhesion strength and corrosion resistance of aluminium alloy (i.e., AA5083) to fibre (i.e., basalt or glass) reinforced composite adhesive joints for nautical applications. Furthermore, some TSA anodized samples were soaked in a NaOH solution to investigate the influence of this post-immersion step on the joint performances. With the aim to improve the fibre-matrix adhesion in the composite substrate thus further increasing the overall mechanical response of the joint, glass and basalt fibres were treated…
Electrochemical Fabrication and Physicochemical Characterization of Metal/High-k Insulating Oxide/Polymer/Electrolyte Junctions
Photoelectrochemical polymerization of poly(3,4-ethylenedioxythiophene), PEDOT, was successfully realized on anodic film grown to 50 V on magnetron sputtered Ti-6 atom % Si alloys. Scanning electron microscopy allowed us to evidence formation of compact and uniform polymer layers on the oxide surface. Photoelectrochemical and impedance measurements showed that photopolymerization allows one to grow PEDOT in its conducting state, while a strong cathodic polarization is necessary to bring the polymer in its p-type semiconducting state. Information on the optical and electrical properties of metal/oxide/polymer/electrolyte junctions proves that PEDOT has promising performance as an electrolyte…
Forming-Free and Self-Rectifying Resistive Switching Effect in Anodic Titanium Dioxide-Based Memristors
The paper presents the resistive switching of electroforming-free Ti/anodic- TiO 2 /Cu memristors. Anodic TiO 2 thin films were prepared by anodizing Ti layers. Microscale devices were fabricated by direct laser-assisted photolithography. Experimental results showed a bipolar and self-rectifying behavior of the devices, which could be useful for crossbar array configurations. Moreover, a gradual resistive switching of the devices in both directions was observed, indicating the presence of multi-level resistance states.
Electroplated bismuth absorbers for planar NTD-Ge sensor arrays applied to hard x-ray detection in astrophysics
Single sensors or small arrays of manually assembled neutron transmutation doped germanium (NTD-Ge) based microcalorimeters have been widely used as high energy-resolution detectors from infrared to hard X-rays. Several planar technological processes were developed in the last years aimed at the fabrication of NTD-Ge arrays, specifically designed to produce soft X-ray detectors. One of these processes consists in the fabrication of the absorbers. In order to absorb efficiently hard X-ray photons, the absorber has to be properly designed and a suitable material has to be employed. Bismuth offers interesting properties in terms of absorbing capability, of low heat capacity (needed to obtain h…
Tailoring of the Solid State Properties of Al–Nb Mixed Oxides: A Photoelectrochemical Study
Al–Nb containing mixed oxides were grown by anodizing sputter-deposited Al–Nb alloys of different compositions. A photoelectrochemical investigation was carried out in order to estimate the band gap, flat band potential, and conductivity type of these oxides as a function of their composition. The dependence of the band gap on the composition of mixed sp–d metal oxides has been rationalized by using a semiempirical correlation between the difference of electronegativity and band gap of oxides proposed in the literature some years ago and recently tested for regular d–d metal mixed oxides. The band gap increase observed as a function of Al content into the oxides seems mainly depending on th…
Corrosion resistance of passive films on different stainless steel grades in food and beverage industry
Abstract Passive films were grown on 304 L, 316 L and Duplex stainless steels by immersion at open circuit potential in solutions mimicking food and beverage industry environments. In acidic food stainless steel surfaces are covered by Cr rich passive films, and generalized dissolution occurs on their surface with consequent ions release into the electrolyte. In fatty food the concentration of released ions is significantly lower since generalized corrosion does not occur, but the loss on MnS inclusions strongly reduces the polarization resistance in this environment especially for 304 L due to its higher localized corrosion susceptibility with respect to the other grades.
Dielectric Properties of Al-Nb Amorphous Mixed Oxides
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Band gap narrowing and dielectric constant enhancement of (NbxTa(1-x))2O5 by electrochemical nitrogen doping
Abstract Anodic films were grown to 5 V and 50 V on Nb, Ta and Ta-Nb sputtering deposited alloys in 0.1 M ammonium biborate solutions in order to induce N incorporation. Their properties were compared to those of N free anodic films grown to the same formation voltages in 0.1 M NaOH. Photoelectrochemical measurements evidenced the presence of optical transitions at energy lower than the band gap of the oxides, attributed to localized states located close to the valence band mobility edge of the films, generated by N 2p orbitals, with consequent narrowing of the band gap. Since N incorporation occurs in the outer 70% of the anodic films, the dependence of the measured photocurrent as a funct…
The influence of nitrogen incorporation on the optical properties of anodic Ta2O5
Abstract Anodic oxides were grown on sputter-deposited Ta in different aqueous solutions. A photoelectrochemical investigation was performed in order to estimate the band gap of the films as a function of the anodizing bath composition and formation voltage, i.e. thickness. Photoelectrochemical results provided evidence of sub-band gap photocurrent for films formed in a bath containing ammonium ions at pH 9. Elemental depth profiles obtained by glow discharge optical emission spectroscopy revealed the presence of nitrogen species in the outer part of the anodic films, which is bonded to Ta according to XPS analysis. A mechanism of nitrogen incorporation is proposed in order to account for t…