Band Gap Modeling of Different Ternary and Quaternary Alumina Garnet Phases Y3(AlXGa1-X)5O12 (YAGG) and Lu3(AlXGa1-X)5O12 (LuAGG). A Semiempirical Approach

A further generalization to quaternary oxide systems of the modeling equation of optical band gap values, based on the semiempirical correlation between the differences in the electronegativity of oxygen and the average cationic electronegativity, proposed some years ago, has been carried out by expanding the approach recently employed for ternary mixed oxides. The choice of oxide polymorphs and their influence on the fitting procedure of an experimental data set is evidenced by a detailed discussion of the fitting process of the literature's experimental band gap data pertaining two quaternary oxide systems of the garnet family, namely, Y3(AlxGa1-x)5O12 (YAGG) and Lu3(AlxGa1-x)5O12 (LuAGG), playing an important role in several engineering applications. The two investigated systems, moreover, span a quite large range of band gap energy values (from similar to 5.5 to similar to 7.5 eV), as a function of the Al/Ga ratio, allowing a rigorous test of the proposed modeling equation. Based on the wide existing literature on the presence of excitonic effects in the investigated systems some empirical correlations between an optical gap and a band gap in the presence of excitonic effects are suggested, too, which could provide some rationale to overcome the discrepancies frequently encountered in comparing band gap values reported in the literature for the same materials. The results of this work confirm the ability of this semiempirical approach in providing good agreement between experimental and theoretical band gap values also for very complex systems, where more sophisticated density functional theory-based methods face some difficulties in predicting the correct values

A Generalized Semiempirical Approach to the Modeling of the Optical Band Gap of Ternary Al-(Ga, Nb, Ta, W) Oxides Containing Different Alumina Polymorphs

A generalization of the modeling equation of optical band gap values for ternary oxides, as a function of cationic ratio composition, is carried out based on the semiempirical correlation between the differences in the electronegativity of oxygen and the average cationic electronegativity proposed some years ago. In this work, a novel approach is suggested to account for the differences in the band gap values of the different polymorphs of binary oxides as well as for ternary oxides existing in different crystalline structures. A preliminary test on the validity of the proposed modeling equations has been carried out by using the numerous experimental data pertaining to alumina and gallia polymorphs as well as the crystalline ternary Ga(1-x)AlxO3 polymorphs (α-Ga(1-x)AlxO3 and β-Ga(1-x)AlxO3) covering a large range of optical band gap values (4.50-8.50 eV). To make a more rigorous test of the modeling equation, we extended our investigation to amorphous ternary oxides anodically formed on Al-d-metal alloys (Al-Nb, Al-Ta, and Al-W) covering a large range of d-metal composition (xd-metal ≥ 0.2). In the last case, the novel approach allows one to overcome some difficulties experienced in fitting the optical band gap dependence from the Al-d-metal mixed anodic oxide composition as well as to provide a rationale for the departure, at the lowest d-metal content (xd-metal < 0.2), from the behavior observed for anodic films containing higher d-metal content

Template electrosynthesis of La(OH)3 and Nd(OH)3 nanowires using porous anodic alumina membranes

High quality arrays of Ln(OH)3 (Ln = La, Nd) nanowires have been successfully fabricated for the first time by an electrochemical process using anodic alumina membrane templates. A physico-chemical characterisation of electrodeposited hydroxides has been carried out by different techniques (XRD, SEM and EDX). The results show that the synthesized nanostructures are crystalline, dense, continuous, well aligned, and with high aspect ratio, suggesting further development of possible applications in the lanthanide family species

Room temperature electrodeposition of photoactive Cd(OH)2 nanowires

Cd(OH)2 nanowires (NWs) were successfully prepared by room temperature electrogeneration of base using Cd(NO3)2 aqueous electrolyte and Anodic Alumina Membrane (AAM) as template. Cd(OH)2 films have been also deposited on tin-doped indium oxide (ITO) for comparison. SEM analysis shows high quality deposits made of closely packed nanowires (NWs) into AAM and uniform flake-like surface on ITO. XRD analysis reveals that Cd(OH)2 films on ITO are polycrystalline, while the nanowires grow along the preferential directions [100] and [110]. Photoelectrochemical measurements show that Cd(OH)2 NWs are photoactive materials with indirect and direct band gap of 2.15 and 2.75 eV, respectively. Keywords: Electrogeneration of base, Cd(OH)2, Nanowires, Band ga

Physicochemical characterization of passive films on niobium by admittance and electrochemical impedance spectroscopy studies

An analysis of the electronic properties of amorphous semiconductor–electrolyte junction is reported for thin (Dox < 20 nm) passive film grown on Nb in acidic electrolyte. It will be shown that the theory of amorphous semiconductor–electrolyte junction (a-SC/El) both in the low band-bending and high band-bending regime is able to explain the admittance data of a-Nb2O5/El interface in a large range (10 Hz–10 kHz) of frequency and electrode potential values. A modelling of experimental EIS data at different potentials and in the frequency range of 0.1 Hz–100 kHz is presented based on the theory of amorphous semiconductor and compared with the results of the fitting of the admittance data obtained in a different experiment. Some preliminary insights on the possible dependence of the density of state (DOS) distribution on the mobile defects concentration and mechanism of growth of anodic film on valve metals are suggested

Recent advances on physico-chemical characterization of passive films by EIS and differential admittance techniques

Thin Nb2O5 anodic films (20 nm thick) grown in phosphoric acid solution have been characterised by EIS and differential admittance study in a large range of potential and frequency. The overall electrical behaviour has been interpreted by means of the theory of amorphous semiconductor Schottky barrier in presence of a non-constant density of states (DOS). A comparison of DOS for films grown in different electrolytes is reported

Physicochemical characterisation of thermally aged anodic films on magnetron sputtered niobium

The influence of thermal aging, at intermediate temperature (1h 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 characterisation of the a-Nb2O5/0.5M H2SO4 electrolyte junction has been carried out by means of photocurrent and electrochemical impedance spectroscopy as well by differential admittance measurements. A change in the optical band gap (3.45 eV) of niobia film has been observed after aging (3.30 eV) at 250°C in air for 1 hour. A cathodic shift (0.15-0.2 Volt) in the flat band potential of the junction has been observed by the differential admittance (DA) measurements carried out in a large range of electrode potential values (6Volt) and ac frequencies (10 Hz-5 kHz). The frequency dependence of DA data, in absence of an appreciable contribution from surface states distribution, agrees with expectations of the theory of amorphous semiconductor Schottky barrier. The fitting of both components of DA allowed to get information on the distribution of electronic density of states (DOS) as a function of energy and distance from metal oxide interface. The DA measurements evidenced for vacuum treated niobia film an insulating to semiconductor transition with possible metallization of the inner metal/oxide interface. 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