M. Santamaria

A critical assessment of the Mott-Schottky analysis for the characterisation of passive film-electrolyte junctions

The widespread use of the Mott-Schottky plots to characterize the energetics of passive film/electrolyte junction is critically reviewed in order to point out the limitation of such approach in describing the electronic properties of passive film as well in deriving the correct location of the characteristic energy levels of the junction. The frequency dependency of M-S plots frequently observed in the experimental data gathered in a sufficiently large range of frequency is extensively discussed for a relatively thick (160 nm) thermally aged amorphous niobia (α-Nb2O5) film immersed in electrolytic solution. The relatively simple equivalent electrical circuit describing an ideally blocking behaviour of the junction allows a direct comparison of the experimental data analysis based on the use of Mott-Schottky or amorphous semiconductor Schottky barrier interpretative models. Moreover the theoretical simulations of the M-S plots based on the theory of crystalline semiconductor suggest an electronic structure of the investigated passive film containing a distribution of localized electronic states deep lying in energy in agreement with the model of amorphous semiconductor Schottky barrier.

The Influence of the Electronic Properties of Passive Films on the Corrosion Resistance of Mo‐Ta Alloys A Photoelectrochemical Study

Photoelectrochemical experiments have been carried out for characterizing passive films on Mo-Ta sputtered alloys having different compositions, as well as on pure Mo and Ta metals. Both corrosion layers, formed by simple immersion in solution, and films grown anodically were investigated. The presence of Mo species in the passive layer anodically shifts the flatband potential with respect to pure Ta{sub 2}O{sub 5} films. For high Mo contents the films change their behavior from an insulating to n-type semiconducting one. A variation in the optical bandgap occurs due to the change of the Mo{sup 6+}/Ta{sup 5+} ratio into the passive films. Cross experiments, performed in different solutions on the same film, suggest that a loss of Mo{sup 6+} ions occurs at the oxide/electrolyte interface under anodic polarization. The influence of Mo content on the electronic properties of the passive films is invoked in order to explain its effect on the corrosion resistance of the different alloys.

Semiconductor electrochemistry approach to passivity and passivity breakdown of metals and metallic alloys

Abstract A critical appraisal of the use of the theory of semiconductors in characterising passive films on metals and alloys is provided, with special emphasis on the use of Mott-Schottky theory for the location of characteristic energy levels of the passive film-electrolyte junction. Some inconsistencies between theory and experimental results in the case of thin passive films are discussed together with possible alternative ways for overcoming such problems. The role of semiconducting properties in determining the pitting behaviour of passive films on W in solutions containing halide is presented and discussed. The validity of a recently proposed correlation between the solid state properties of passive films and the pitting potential is critically reviewed.

Recent advances in photocurrent spectroscopy of passive films

Abstract The quantitative application of photocurrent spectroscopy (PCS) for the in-situ determination of the composition of passive films and corrosion layers is reviewed in the light of recent theoretical advances, that have allowed to relate the measured optical gaps to the Pauling electronegativities of the film components. The correlations derived are tested versus recent experimental results regarding mixed oxides, anhydrous passive films on metallic alloys and hydroxide layers. The effect of the eventual long-range disorder into the passive film on the optical band gap values is also discussed. New experimental evidence reported for mixed d,d-metal oxides and passive films on sp,d-metal alloys gives satisfactory agreement with the theoretical expectations. The experimental results evidence the role of the alloying metal in determining the crystalline or disordered structure of passive films grown on Al,d-metal alloys.

A semiempirical correlation between the optical band gap of hydroxides and the electronegativity of their constituents

In analogy with previous results on anhydrous oxides, a correlation is proposed between the optical band gap of hydroxides and the electronegativities of their constituents. Based on the experimental results on passive hydrated layers on metals obtained in our laboratory and the literature data, it is found that the hydroxide band gap varies with the square of the difference between the electronegativities of the metallic cation and the hydroxyl group. Like in the case of anhydrous oxides, two different interpolation lines have been found forsp-metal andd-metal hydroxides, respectively. The proposed correlations predict semiconducting or insulating behavior even for the most electronegative metals, at variance with the case of oxides of noble metals, for which the observed metallic behavior is foreseen.

Effect of Composition on the Photoelectrochemical Behavior of Anodic Oxides on Binary Aluminum Alloys

The photoelectrochemical behavior of anodic films on Al alloys, containing titanium, tantalum, and tungsten (valve metals), has been studied as a function of alloy composition and anodizing conditions. Photocurrent spectroscopy has been used to get information on bandgap and the flatband potential values of different mixed oxides. Both insulator-like and semiconducting behavior has been observed for anodic oxides grown on Al-W and Al-Ti alloys dependent on alloy initial composition. Optical bandgap values, E opt g , of different oxides are in accordance with predictions based on the correlation between E opt g and the difference of electronegativities of the oxide constituents, indicating potential for tailoring solid state properties of ternary oxides.

Physicochemical Characterization of Thermally Aged Anodic Films on Magnetron-Sputtered Niobium

The influence of thermal aging, at intermediate temperature (1 h at 250°C) and in different environments, on the electronic and solid-state properties of stabilized 160 nm thick amorphous anodic niobia, grown on magnetron-sputtered niobium metal, has been studied. A detailed physicochemical characterization of the a-Nb 2 O 5 /0.5 M H 2 SO 4 electrolyte junction has been carried out by means of photocurrent and electrochemical impedance spectroscopy as well as by differential admittance (DA) measurements. A change in the optical bandgap (3.45 eV) of niobia film has been observed after aging (3.30 eV) at 250°C in air for 1 h. A cathodic shift (0.15-0.2 V) in the flatband potential of the junction has been observed. The frequency dependence of DA data agrees with expectations of the theory of amorphous semiconductor Schottky barner. The fitting of both components of DA allowed to get information on the distribution of the electronic density of states as a function of energy and distance from the metal oxide interface. The DA measurements evidenced for vacuum-treated niobia film an insulating to semiconductor transition. These findings can help to explain the large changes in the measured values of capacitance, after aging, and the larger leakage current observed in niobia electrolytic capacitors.

Photocurrent spectroscopy study of passive films on hafnium and hafnium-tungsten sputtered alloys

Abstract Anodic and air-formed films on sputtered Hf and W–Hf alloys of different composition have been investigated by Rutherford back scattering, photocurrent spectroscopy (PCS) and transmission electron microscopy (TEM) techniques. In alkaline solutions the PCS data suggest the formation on Hf metal of a duplex layer with anodic hafnia covered by an external layer of composition close to HfO(OH) 2 . This last compound is also present on Hf air-formed films. In acidic solutions the initial oxy-hydroxide film disappears at high anodising potentials ( V f >10 V). In the case of W–Hf alloys films of different composition and semiconducting behaviour are formed by air exposure or by anodising in different electrolytes. A PCS analysis of films grown on sputtered alloys is performed on the basis of previously proposed correlation between the band gap of anodic films and difference of electronegativity of their constituents.

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 suggested in the literature to use mixed inorganic–organic thin film transistors by assembling a structure formed by metal bottom contact/dielectric layer gate/organic semiconductor/top contact source/drain. According to this, a wet electrochemical route appears to be very promising in terms of cost, at least for the preparation of thin thickness 10 nm or thick thickness 10 nm oxide films by anodizing in aqueous electrolytes. Moreover, by taking into account the possibility to grow semiconducting polymers on wide bandgap dielectric oxide Ta2O5 by a photoelectrochemical route, which has been shown recently, 5,6 it seems very appealing to exploit an integral electrochemical route to fabricate advanced inorganic/organic hybrid structure which could be used as a building block for a field effect transistor FET junction. In this paper, we describe and discuss the electrochemical fabrication of a hybrid structure to be used in the production of an inorganic–organic field effect transistor IOFET using 3,4polyethylenedioxythiophene PEDOT as a semiconducting polymer and anodic films grown on the Ti-10 atom % Zr alloy as dielectrics. The choice of the oxide is based on its low dark current value and quite high photocurrent intensity, under monochromatic light, at not too high anodic potential and photon energy, 7 as well as on its high dielectric permittivity 45, according to Ref. 8. The metal/oxide/ polymer junctions are investigated by photocurrent spectroscopy PCS and scanning electron microscopy SEM. Finally, output transistor characteristics are recorded in order to test the performance of the junctions in the IOFET structure. Experimental Ti-10 atom % Zr alloys were prepared by dc magnetron sputtering. Targets consisted of 99.9% zirconium disk, of 100 mm diameter, with an appropriate number of 99.9% titanium disks, of 20 mm diameter, located symmetrically on the erosion region for the preparation of the alloys. Substrates used were glass plates. 8 The composition of the alloy was determined by Rutherford backscattering

An Electrochemical Investigation on the Adhesion of As-Formed Anodic TiO2 Nanotubes Grown in Organic Solvents

nanotubes formed in ethylene glycol were investigated in aqueoussolutions by considering for the first time a new barrier layer formation between nanotubes and titanium substrate which affectstheir behavior and more importantly, measured properties thereof. Dissolution of titanium fluoride layer between nanotubes andsubstrate in aqueous solutions results in detachment of nanotubes from substrate and formation of a new barrier layer on titaniumsurface by anodic polarization. We have shown that photoelectrochemical properties of nanotubes after polarization in aqueoussolutions are influenced to a great extent by properties of the newly formed layer.© 2010 The Electrochemical Society. DOI: 10.1149/1.3509123 All rights reserved.Manuscript submitted September 2, 2010; revised manuscript received October 11, 2010. Published November 9, 2010.