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Coatings were grown on the AZ31 Mg alloy by a hard anodizing process in the hot glycerol phosphate-containing electrolyte. Anodizing conditions were optimized, maximizing corrosion resistance estimated by impedance measurements carried out in Hank's solution at 37 °C. A post anodizing annealing treatment (350 °C for 24 h) allowed us to further enhance the corrosion resistance of the coatings mainly containing magnesium phosphate according to energy-dispersive X-ray spectroscopy and Raman analyses. Gravimetric measurements revealed a hydrogen evolution rate within the limits acceptable for application of AZ31 in biomedical devices. In vitro tests demonstrated that the coatings are biocompatible with a preosteoblast cell line.

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 band potential were revealed for the porous oxide on the alloy. The different electronic properties were rationalized by taking into account the presence of localized states inside the gap, induced by incorporation of Al and V from the underlaying alloy during the hard anodizing process. These electronic properties are responsible of the reactivity of porous layer grown on Ti6Al4V alloy in simulated body fluid.

Anodic oxides were grown to 50V on Ta in several organic ions containing anodizing baths. Their properties were compared with anodic Ta oxide film grown to the same formation voltage in 0.1M NaOH. Anodizing process carried out in sodium citrate led to the growth of the anodic oxide with the best blocking properties whilst, when Ta is anodized in sodium adipate, a significant part of the circulated charge is wasted in side reactions, such as oxygen evolution. Photoelectrochemical measurements showed the presence of optical transitions at energy lower than the band gap for the anodic films grown in citrate and tartrate electrolytes, attributed to localized electronic states located close to the valence band mobility edge of the films generated by anions incorporation into the oxide. Differential capacitance measurements proved an increase by 17% in capacitance value for the oxide grown in citrate-containing solution with respect to that grown in NaOH electrolyte. A sketch of the energetic of the metal/oxide interface is provided.

Redox-based resistive switching memories (ReRAMs) are the strongest candidates for next generation nonvolatile memories. These devices are commonly composed of metal/solid electrolyte/metal junctions, where the solid electrolyte is usually an oxide layer. A key aspect in the ReRAMs development is the solid electrolyte engineering, since it is crucial to tailor the material properties for obtaining excellent switching properties (e.g. retention, endurance, etc.). Here we present an anodizing process as a non vacuum and low temperature electrochemical technique for growing oxides with tailored structural and electronic properties. The effect of the anodizing conditions on the solid state properties of the anodic oxides is studied in relation to the final ReRAM device performances demonstrating the great potentiality of this technique to produce high quality oxide thin films for resistive switching memories.

Redox-based resistive switching memories (ReRAM) based on metal oxides are considered as the next generation non-volatile memories and building units for neuromorphic computing. Using different deposition techniques results however in different structural and electric properties, modulating the device performance. In this study HfO2 and Nb2O5 were prepared electrochemically by anodizing sputtering-deposited Hf and Nb in borate buffer solution. Photoelectrochemical measurements were used to study the solid state properties of the anodic oxides, such as band gap and flat band potential. In the case of anodic HfO2, detected photocurrent is ascribed to optical transitions between localized (generated by the presence of oxygen vacancies into the oxide) and extended states. Impedance measurements disclosed the formation of n-type Nb2O5 and insulating HfO2. Pt top electrode was deposited onto the metal/anodic oxide junctions to fabricate ReRAM cells. Whereas switching behaviour of Nb/anodic Nb2O5/Pt cells was not reliable, good endurance and retention performances were proved in the case of Hf/anodic HfO2/Pt cells, showing that electrochemical growth of the oxides can be a reliable way to fabricate solid electrolytes for resistive switching memories.

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 their application in different technological fields, such as coatings for corrosion protection and as dielectrics for electrolytic capacitors or as gate oxides in thin film field effect transistors (MOS-FET).

Anodic films were grown to 5 V (Ag/AgCl) on mechanically polished Hf in 0.1 M ammonium biborate and 0.1 M NaOH. Independent of the anodizing conditions, the photoelectrochemical characterization allowed the observation of optical transitions at 3.25 eV, i.e. at photon energy lower than the bandgap of HfO2. They are attributed to localized states inside the gap of the oxide induced by the presence of oxygen vacancies. From the cathodic photocurrent spectra, it was possible to estimate an energy threshold of ∼2.15 eV for internal electron photoemission phenomena. The impedance measurements proved the formation of insulating oxides with ϵ =19. The anodizing occurs under a high field regime with an activation energy of 1.1 eV and an activation distance of 3.8 Å.

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 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.

Redox-based resistive switching memories (ReRAMs) are strongest candidates for the next-generation nonvolatile memories fulfilling the criteria for fast, energy efficient, and scalable green IT. These types of devices can also be used for selector elements, alternative logic circuits and computing, and memristive and neuromorphic operations. ReRAMs are composed of metal/solid electrolyte/metal junctions in which the solid electrolyte is typically a metal oxide or multilayer oxides structures. Here, this study offers an effective and cheap electrochemical approach to fabricate Ta/Ta2O5-based devices by anodizing. This method allows to grow high-quality and dense oxide thin films onto a metallic substrates with precise control over morphology and thickness. Electrochemical-oxide-based devices demonstrate superior properties, i.e., endurance of at least 106 pulse cycles and/or 103I–V sweeps maintaining a good memory window with a low dispersion in ROFF and RON values, nanosecond fast switching, and data retention of at least 104 s. Multilevel programing capability is presented with both I–V sweeps and pulse measurements. Thus, it is shown that anodizing has a great prospective as a method for preparation of dense oxide films for resistive switching memories.

Anodic films of different thickness (∼30 nm and 70 nm) were grown by anodizing sputtering-deposited Ta-19at% Al to different formation voltages. N incorporation into the anodic films was inducing by performing the anodizing process in ammonium containing solutions. Layered anodic films were prepared by a double formation procedure with a first anodizing step in ammonium biborate solution and second anodizing step in borate buffer solution, or vice versa. Glow Discharge Optical Emission Spectroscopy was employed to show the distribution of N across the oxide. Photoelectrochemical measurements evidenced a red shift of the light absorption threshold due to N incorporation. A model was proposed and tested to model the dependence of quantum yield on photon energy and, thus, to estimate the band gap of the layers for both anodized Ta and Ta-19at% Al.

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 internal photoemission processes of electrons resulted to be independent of the anodizing electrolyte confirming that N incorporation does not appreciably affect the density of states distribution close to the conduction band mobility edge. The transport of photogenerated carriers has been rationalized according to the Pai–Enck model of geminate recombination.

Al-Ta mixed oxides were grown by anodizing sputter-deposited Al-Ta alloys of different composition. Photocurrent spectra revealed a band gap, Eg, slightly independent on Ta content and very close to that of anodic Ta2O5 (∼4.3 eV) with the exception of the anodic film on Al-10at% Ta, which resulted to be not photoactive under strong anodic polarization. The photoelectrochemical characterization allowed to estimate also the oxides flat band potential and to get the necessary information to sketch the energetic of the metal/oxide/electrolyte interfaces. Impedance measurements allowed to confirm the formation of insulating material and to estimate the dielectric constant of the oxides, which resulted to be monotonically increasing with increasing Ta content (from 9 for pure Al2O3 to 30 for pure Ta2O5).