Effect of 100 KeV Ar+ ion beam irradiation on ZnO thin films – Influence of morphology vis-a-vis electrode/electrolyte interface and its impact on photoelectrochemical water splitting

The present study attempts quantitative determination of changes in the morphological surface features viz. fractal dimension, lower and upper cut off length scale through Power Spectral Density analysis prior to and after irradiation of 100 KeV Ar⁺ ion beam at incidence angles of 0°, 40° and 60° on ZnO thin films. All the unirradiated and irradiated samples are subjected to photoelectrochemical characterization and a correlation between photoelectrochemical performance and morphological parameters is established. Sample irradiated at 40° angle at the fluence of 5 × 10¹⁶ ions/cm² is found to possess maximum fractal dimension of 2.72, lower and upper cut off length scale of 3.16 nm and 63.00 nm respectively. This sample exhibits maximum photocurrent density of 3.19 mA/cm² and applied bias photon-to-current efficiency of 1.12% at 1.23 V/RHE. Hydrogen gas collected for duration of 1 h for the same sample was ~4.83 mLcm^?2.     

Augmented photoelectrochemical response of CdS/ZnS quantum dots sensitized hematite photoelectrode

A visible light active and stable photoelectrode has been developed by depositing a passivating layer of ZnS QDs on CdS QDs sensitized hematite photoelectrode (Hematite‐CdS/ZnS) for PEC generation of hydrogen. Photoelectrochemical properties, in terms of stability and efficiency, have been investigated on the various hematite photoelectrodes sensitized with CdS QDs and CdS/ZnS QDs by varying number of SILAR cycles. I–V characteristics show that two layers of ZnS QDs deposited over three layers of CdS could enhance PEC response of hematite and efficiency by a factor of 3 and 11 respectively. Chronoamperometry measurement ensures that after adding a layer of ZnS QDs, CdS sensitized hematite film turns out to be a stable photoelectrode in the electrolyte. Prepared photoelectrodes have been characterized by XRD, SEM, HRTEM and UV–Vis spectrophotometer for various structural, morphological and optical properties to analyze PEC results. Mott–Schottky analysis and incident photon to current conversion efficiency (IPCE) measurements of sensitized hematite photoelectrode supported the improved PEC response of CdS/ZnS QDs sensitized hematite thin films. Copyright © 2016 John Wiley & Sons, Ltd.     

Design and synthesis of foam glasses from recycled materials

Recycling has emerged as an environmental key point due to the diminishing of natural resources and the generation of ever-increasing amounts of industrial solid wastes. Glass wastes are among the materials that attract great interest in the recycling concept. This work presents the results of foams production from four series of compositions. The first series comprises powders of a sodium-calcium-silicate sheet glass cullet as the main component, an alkali-earth aluminosilicate glass as an additive, and a reagent grade silicon carbide (SiC) powder as gassing agent. In the second series, the glass cullet was used in combination with fly ashes (FLA) as main components, while SiC waste from abrasive paper served as foaming agent. In the third and fourth series, carbonates (calcite and dolomite) were used for foaming powder mixtures composed of sheet glass cullet and FLA, and powdered cathode ray tube panel glasses, respectively. All the processing parameters, including the main components, the nature and content of foaming agents are shown to play a crucial role on the foaming ability and final properties of the glass foams.     

Nanostructured Zn-Fe2O3 thin film modified by Fe-TiO2 for photoelectrochemical generation of hydrogen

Nanostructured semiconductor thin films of Zn-Fe₂O₃ modified with underlying layer of Fe-TiO₂ have been synthesized and studied as photoelectrode in photoelectrochemical (PEC) cell for generation of hydrogen through water splitting. The Zn-Fe₂O₃ thin film photoelectrodes were designed for best performance by tailoring thickness of the Fe-TiO₂ film. A maximum photocurrent density of 748 μA/cm² at 0.95 V/SCE and solar to hydrogen conversion efficiency of 0.47% was observed for 0.89 μm thick modified photoelectrode in 1 M NaOH as electrolyte and under 1.5 AM solar simulator. To analyse the PEC results the films were characterized for various physical and semiconducting properties using XRD, SEM, EDX and UV–Visible spectrophotometer. Zn-Fe₂O₃ thin films modified with Fe-TiO₂ exhibited improved visible light absorption. A noticeable change in surface morphology of the modified Zn-Fe₂O₃ film was observed as compared to the pristine Zn-Fe₂O₃ film. Flatband potential values calculated from Mott–Schottky curves also supported the PEC response.     

An Analytical 1-D Model for Ion Implantation of Any Species into Single-Crystal Silicon Based on Legendre Polynomials

A computationally-efficient 1-D analytical model for ion implantation of any species into single crystal silicon is presented. By interpolating between a few species, the model can predict as-implanted profiles for all the other species. The model uses Legendre polynomials as basis functions. The results of the model are in good agreement with UT-MARLOWE, which is a physically-based and experimentally verified Monte Carlo simulator.     

A universal ion implantation model for all species intosingle-crystal silicon

A physically based model for ion implantation of any species into single crystal silicon has been developed, tested and implemented in the ion implant simulator, UT-MARLOWE. In this model, an interpolation scheme, based on mathematical properties of ion-target interatomic potential, was employed and implemented to calculate the scattering process. Using this scheme, the resulting energy, direction and momentum of the ion and target can be derived from the existing scattering tables of UT-MARLOWE without calculating the entire scattering process. The method has advantages in terms of both accuracy and computational efficiency, as well as significantly reduced cost of code development. The impurity profiles and damage profiles predicted by the model simulations have been compared with secondary ion mass spectroscopy (SIMS) and Rutherford backscattering spectrometry (RBS), and excellent agreement with experimental data has been achieved     

Role of vanadium oxide on the lithium silicate glass structure and properties

The structural role of V in 28Li₂O–72SiO₂ (in mol%) lithium silicate glass doped with 0.5 mol% V₂O₅ was assessed using ²⁹Si and ⁵¹V Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V₂O₅ used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V₂O₅ addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the ²⁹Si NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V₂O₅ acting as network former, capable to form various tetrahedral units (for n = 0, 1, and 2) in the glasses. These units, which are similar to phosphate units, scavenge the Li⁺ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.     

Spray pyrolytically deposited nanoporous Ti doped hematite thin films for efficient photoelectrochemical splitting of water

Nanoporous hematite (α-Fe₂O₃) thin films doped with Ti⁴⁺ deposited by spray-pyrolysis were successfully used in photoelectrochemical splitting of water for solar hydrogen production. X-ray diffraction, field emission scanning electron microscopy, UV–visible absorption and photoelectrochemical studies have been performed on the undoped and Ti⁴⁺ doped hematite thin films. Morphology of α-Fe₂O₃ thin films was observed to be nanoporous, with increased porosity (pore size ∼12 to 20 nm) on increasing doping concentration. A significant decrease in the bandgap energy from 1.95 to 1.27 eV was found due to doping. α-Fe₂O₃ film doped with 0.02 M Ti⁴⁺ ions exhibited best solar to hydrogen conversion efficiency (photoconversion efficiency) of 1.38% at 0.5 V/SCE. Highest photocurrent densities of 0.34 mA/cm² at zero bias and 1.98 mA/cm² at 0.5 V/SCE were obtained by incorporating 0.02 M Ti⁴⁺ in α-Fe₂O₃, which are significantly larger than earlier reported values. Donor density (30.8 × 10²⁰ cm⁻³) and flatband potential (−1.01 V/SCE) obtained were also maximum for this sample. Hydrogen collected in 1 hr at Pt electrode with the best photoelectrode was 2.44 mL with 150 mW/cm² visible light source.     

Experimental and first-principles studies of BiVO4/BiV1-xMnxO4-y n-n+ homojunction for efficient charge carrier separation in sunlight induced water splitting

Though bismuth vanadate (BiVO₄) is extensively used as a photoactive material, its performance in harnessing solar energy is limited by ineffective separation of photo-excited charge carriers. We demonstrate here a concept of n-n⁺ homojunction of BiVO₄/BiV_1-xMn_xO_4-y, which improves its charge separation efficiency. Using first-principles theoretical calculations, we determine the effect of Mn substitution on oxygen vacancy formation energies and associated changes in the electronic structure of BiVO₄. Showing that Mn substitution pushes the Fermi level of BiVO₄ towards its conduction band, we predict that the associated enhanced bending of bands at the homojunction (BiVO₄/BiV_1-xMn_xO_4-y) facilitates efficient separation of charge carriers. With Mott-Schottky experiments, we verify the increased band bending at the n-n⁺ homojunction, and show that the maximum photocurrent density measured in a sample with n-n⁺ homojunction is ten times higher than that obtained of the pristine sample. Secondly, Mn substitution in BiVO₄ also reduces the oxygen vacancy formation energy, promoting higher concentration of O-vacancies, further enhancing the photoelectrochemical response.     

Colorimetric sensor for triphosphates and their application as a viable staining agent for prokaryotes and eukaryotes

The chromogenic complex 1 x Zn (where 1 is (E)-4-(4-dimethylamino-phenylazo)-N,N-bispyridin-2-ylmethyl-benzenesulfonamide) showed high affinity toward the phosphate ion in tetrabutylammonium phosphate in acetonitrile solution and could preferentially bind to adenosine triphosphate (ATP) in aqueous solution at physiological pH. This binding caused a visual change in color, whereas no such change was noticed with other related anions (adenosine monophosphate, adenosine diphosphate, pyrophosphate, and phosphate) of biological significance. Thus, 1 x Zn could be used as a staining agent for different biological cells through binding to the ATP, generated in situ by the mitochondria (in eukaryotes). For prokaryotes (bacteria) the cell membrane takes care of the cells' energy conversion, since they lack mitochondria. ATP is produced in their unique cell structure on the cell membrane, which is not found in any eukaryotes. These stained cells could be viewed with normal light microscopy. This reagent could even be used for distinguishing the gram-positive and the gram-negative bacteria (prokaryotes). This dye was found to be nonlipophilic in nature and nontoxic to living microbes (eukaryotes and prokaryotes). Further, stained cells were found to grow in their respective media, and this confirmed the maintenance of viability of the microbes even after staining, unlike with many other dyes available commercially.