Genesis and Propagation of Fractal Structures During Photoelectrochemical Etching of n-Silicon

The genesis, propagation, and dimensions of fractal-etch patterns that form anodically on front- or back-illuminated n-Si(100) photoelectrodes in contact with 11.9 M NH₄F(aq) has been investigated during either linear-sweep voltammetry or when the electrode was held at a constant potential (E = +6.0 V versus Ag/AgCl). Optical images collected in situ during electrochemical experiments revealed the location and underlying mechanism of initiation and propagation of the structures on the surface. X-ray photoelectron spectroscopic (XPS) data collected for samples emersed from the electrolyte at varied times provided detailed information about the chemistry of the surface during fractal etching. The fractal structure was strongly influenced by the orientation of the crystalline Si sample. The etch patterns were initially generated at points along the circumference of bubbles that formed upon immersion of n-Si(100) samples in the electrolyte, most likely due to the electrochemical and electronic isolation of areas beneath bubbles. XPS data showed the presence of a tensile-stressed silicon surface throughout the etching process as well as the presence of SiO_xF_y on the surface. The two-dimensional fractal dimension D_(f,2D) of the patterns increased with etching time to a maximum observed value of D_(f,2D)=1.82. Promotion of fractal etching near etch masks that electrochemically and electronically isolated areas of the photoelectrode surface enabled the selective placement of highly branched structures at desired locations on an electrode surface

XPS studies on dispersed and immobilised carbon nitrides used for dye degradation

Liquid phase adsorption is a common technique in waste water purification. However, this process has some downsides. The removal of environmentally harmful contaminants from organic liquids by adsorption produces secondary waste which has to be treated afterwards. The treatment can be e.g. high temperatures or a landfill. Photocatalysts such as CN6 can remove the dye under light irradiation but most times they have to be separated afterwards. Immobilisation of these photocatalysts can be one way to address this problem. The resulting photocatalyst layers were analysed in operando by near-ambient pressure XPS. This enabled us to detect the active species, i.e. oxygen radicals, at the surface, responsible for the dye degradation.TU Berlin, Open-Access-Mittel - 201

Genesis and Propagation of Fractal Structures During Photoelectrochemical Etching of n-Silicon

The genesis, propagation, and dimensions of fractal-etch patterns that form anodically on front- or back-illuminated n-Si(100) photoelectrodes in contact with 11.9 M NH₄F(aq) has been investigated during either linear-sweep voltammetry or when the electrode was held at a constant potential (E = +6.0 V versus Ag/AgCl). Optical images collected in situ during electrochemical experiments revealed the location and underlying mechanism of initiation and propagation of the structures on the surface. X-ray photoelectron spectroscopic (XPS) data collected for samples emersed from the electrolyte at varied times provided detailed information about the chemistry of the surface during fractal etching. The fractal structure was strongly influenced by the orientation of the crystalline Si sample. The etch patterns were initially generated at points along the circumference of bubbles that formed upon immersion of n-Si(100) samples in the electrolyte, most likely due to the electrochemical and electronic isolation of areas beneath bubbles. XPS data showed the presence of a tensile-stressed silicon surface throughout the etching process as well as the presence of SiO_xF_y on the surface. The two-dimensional fractal dimension D_(f,2D) of the patterns increased with etching time to a maximum observed value of D_(f,2D)=1.82. Promotion of fractal etching near etch masks that electrochemically and electronically isolated areas of the photoelectrode surface enabled the selective placement of highly branched structures at desired locations on an electrode surface

Optimized immobilization of ZnO:Co electrocatalysts realizes 5% efficiency in photoassisted splitting of water

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Correction: There is an error in Fig. 8 of the manuscript. The correct Fig. 8 is shown in the additional file. To cite the Correction refer to DOI:10.1039/c6ta90030e.Organic solvents with varied electrophoretic mobility have been employed for deposition of nanocrystalline ZnO: Co particles onto fluorinated tin oxide supports. Evaluation of the electrochemical activity for the oxygen evolution reaction proves a clear solvent-dependence with highest activity upon deposition from acetonitrile and lowest activity upon deposition from ethanol. Analysis of the resulting layer thickness and density attributes the improved electrochemical activity of acetonitrile-prepared samples to larger film thicknesses with lower film densities, i.e. to films with higher porosity. The findings suggest that the ZnO: Co films represent an initially nanocrystalline system where the catalytic activity is predominantly confined to a thin surface region rather than to comprise the entire volume. Closer inspection of this surface region proves successive in operando transformation of the nanocrystalline to an amorphous phase during evolution of oxygen. Furthermore, less active but highly transparent ZnO: Co phases, prepared from ethanol-containing suspensions, can be successfully employed in a stacking configuration with a low-cost triple-junction solar cell. Thereby, a solar-to-hydrogen efficiency of 5.0% in splitting of water at pH 14 could be realized. In contrast, highly light-absorbing acetonitrile/acetone-prepared samples limit the efficiency to about 1%, demonstrating thus the decisive influence of the used organic solvent upon electrophoretic deposition. Stability investigations over several days finally prove that the modular architecture, applied here, represents an attractive approach for coupling of highly active electrocatalysts with efficient photovoltaic devices.BMBF, 03IS2071F, Light2Hydrogen - Energien für die ZukunftDFG, SPP 1613, Regenerativ erzeugte Brennstoffe durch lichtgetriebene Wasserspaltung: Aufklärung der Elementarprozesse und Umsetzungsperspektiven auf technologische Konzept

Solar hydrogen evolution using metal-free photocatalytic polymeric carbon nitride/CuInS2 composites as photocathodes

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Polymeric carbon nitride (g-C3N4) films were synthesized on polycrystalline semiconductor CuInS2 chalcopyrite thin film electrodes by thermal polycondensation and were investigated as photocathodes for the hydrogen evolution reaction (HER) under photoelectrochemical conditions. The composite photocathode materials were compared to g-C3N4 powders and were characterized with grazing incidence X-ray diffraction and X-ray photoemission spectroscopy as well as Fourier transform infrared and Raman spectroscopies. Surface modification of polycrystalline CuInS2 semiconducting thin films with photocatalytically active g-C3N4 films revealed structural and chemical properties corresponding to the properties of g-C3N4 powders. The g-C3N4/CuInS2 composite photocathode material generates a cathodic photocurrent at potentials up to +0.36 V vs. RHE in 0.1 M H2SO4 aqueous solution (pH 1), which corresponds to a +0.15 V higher onset potential of cathodic photocurrent than the unmodified CuInS2 semiconducting thin film photocathodes. The cathodic photocurrent for the modified composite photocathode materials was reduced by almost 60% at the hydrogen redox potential. However, the photocurrent generated from the g-C3N4/CuInS2 composite electrode was stable for 22 h. Therefore, the presence of the polymeric g-C3N4 films composed of a network of nanoporous crystallites strongly protects the CuInS2 semiconducting substrate from degradation and photocorrosion under acidic conditions. Conversion of visible light to hydrogen by photoelectrochemical water splitting can thus be successfully achieved by g-C3N4 films synthesized on polycrystalline CuInS2 chalcopyrite electrodes.BMBF, 03IS2071D, Light2Hydroge

Sustained Water Oxidation by Direct Electrosynthesis of Ultrathin Organic Protection Films on Silicon

Artificial photosynthesis allows exceeding the efficiency and stability limits of natural photosynthesis. Based on the use of semiconducting absorbers, high efficiency in water photolysis has been achieved in various photoelectrode configurations. However, integrated systems are limited in their stability, and more stable half-cell electrodes use protection films prepared by laborious methods. Herein, the facile low-temperature preparation of ultrathin organic protection coatings is demonstrated. The formation is based on the catalytic properties of water oxidation catalysts toward alcohol-polymerization reactions, which results in the formation of hitherto unknown protection layers on silicon. The interfacial layers are generated via iodine-mediated electro-reductive polymerization of ethanol, concomitantly forming during electrophoretic transport of RuO_2 onto silicon supports. Reaction chemistry analyses show that the RuO_2-induced catalysis introduces E2-elimination reactions which result in a carbon sp^3 –sp^2 transformation of the film. For the two modes of photoelectrochemical operation, the photovoltaic and the photoelectrocatalytic mode, 20 and 15 mA cm^(−2) photocurrent densities, respectively, are obtained with unaltered output for 8 and 24 h. The interfacial layer enables Si photovoltages of 500 mV, demonstrating extraordinary electronic interface quality. Since only hydrogen termination of the surface is a prerequisite for growth of the organic protection layer, the method is applicable to a wide range of semiconductors

Oberflächenanalytische Charakterisierung Horizontaler und Vertikaler Nanotopographien an der Silicium/Siliciumoxid/Elektrolyt Phasengrenzfläche

Nanotopography development induced by photoelectrochemical in situ conditioning of silicon is followed using a combination of surface sensitive analysis techniques. In an etching study, vertical nanostructure analysis reveals a buried stressed layer within silicon, identified by Brewster-angle analysis (BAA). In conjunction with in system synchrotron radiation photoelectron spectroscopy (SRPES), a superior quality hydrogen terminated Si(111) surface could be prepared by obliteration of the intermediate stressed layer. Using a novel photoelectrochemical structure formation method, a variety of vertical nanotopographies has been generated and analyzed by in situ Brewster-angle reflectometry (BAR) and scanning probe microscopy (SPM). Shaping of the nanostructures became possible by real-time monitoring using BAR. Appearances range from aligned single nanoislands with improved aspect ratio to connected Si nano-networks. A model was developed to describe the nanostructure formation based on stress-induced selective oxidation. Increased local photo-oxidation is found to result in the formation of extended horizontal micro- and nanostructures with fractal properties. Within a defined light intensity range, the structures reveal the azimuthal symmetry of the investigated crystal planes (111), (100), (110) and (113). The observed features could be reproduced using a model that is based on the interplay of stress in silicon, oxidation by light generated excess holes and locally increased etching in fluoride containing solution.Die durch photoelektrochemische in situ Verfahren induzierte Nanostrukturbildung auf Silicium wird durch eine Kombination oberflächenempfindlicher Methoden untersucht. Durch schrittweise Abtragung eines Oberflächenoxids und durch die Analyse vertikaler Nanostrukturen wird eine verborgene Streßschicht mit Hilfe der Brewster-Winkel Analyse ermittelt. In Verbindung mit Synchrotron-Photoelektronenspektroskopie kann eine optimierte H-Terminierung von Si(111)-Oberflächen nach Entfernen des gestreßten Bereiches erzielt werden. Durch Anwendung einer neuartigen photoelektrochemischen Methode wurde eine Vielzahl vertikaler Nanostrukturen erzeugt, deren Morphologie Aspekt-optimierte nanoskopische Inseln sowie Nanostruktur-Netzwerke umfaßt. In Modellbetrachtungen wird eine streß-induzierte selektive Oxidation als Bildungsmechanismus vorgeschlagen. Verstärkte lokale Photooxidation wiederum führt zur Bildung ausgebreiteter Mikro- und Nanostrukturen, die in einem mittleren Bereich der Lichtintensität die azimutale Symmetrie der jeweiligen (111), (100), (110) und (113) Kristallorientierungen widerspiegeln. Modellhafte Simulationen basieren auf der Wechselwirkung von Streß im Siliciumkristall, lichtgenerierter Oxidation und erhöhter lokaler Materialabtragung in konzentrierter Ammoniumfluoridlösung

Brewster-Angle Variable Polarization Spectroscopy of Colloidal Au-Nanospheres and -Nanorods at the Silicon Surface

Colloidal Au-nanospheres and -nanorods were chemically synthesized from chloroauric acid containing solutions and adsorbed to hydrogen-terminated p-Si(111) surfaces. A comparative analysis of the respective plasmon resonance modes, in solution and at the silicon surface, was carried out by in situ optical transmission and surface reflection techniques. In solution, the absorbance was determined by VIS transmission spectroscopy and compared to Mie theory as well as finite difference time domain calculations. At the p-Si(111) surface, the reflectance was analyzed for the first time by Brewster-angle variable polarization spectroscopy (BA-VPS) and discussed in terms of anisotropic uniaxial thin-film properties. With BA-VPS, the strengths of parallel and orthogonal electric field components of the incident wave can be varied relative to the surface plane. Consequently, opposite changes of transverse and longitudinal resonance strengths are detected upon gradually incremented light polarization angles. Model considerations confirm that spherical and elongated particles can thereby be distinguished. The influence of particle–surface interaction and the dielectric environment is finally discussed

Hydrophobic Nanoreactor Soft-Templating: A Supramolecular Approach to Yolk@Shell Materials

International audienceDue to their unique morphology-related properties, yolk@shell materials are promising materials for catalysis, drug delivery, energy conversion, and storage. Despite their proven potential, large-scale applications are however limited due to demanding synthesis protocols. Overcoming these limitations, a simple softtemplated approach for the one-pot synthesis of yolk@shell nanocomposites and in particular of multicore metal nanoparticle@metal oxide nanostructures (M NP @MO x ) is introduced. The approach here, as demonstrated for Au NP @ITO TR (ITO TR standing for tin-rich ITO), relies on polystyrene- block -poly(4- vinylpyridine) (PS- b -P4VP) inverse micelles as two compartment nanoreactor templates. While the hydrophilic P4VP core incorporates the hydrophilic metal precursor, the hydrophobic PS corona takes up the hydrophobic metal oxide precursor. As a result, interfacial reactions between the precursors can take place, leading to the formation of yolk@shell structures in solution. Once calcined these micelles yield Au NP @ITO TR nanostructures, composed of multiple 6 nm sized Au NPs strongly anchored onto the inner surface of porous 35 nm sized ITO TR hollow spheres. Although of multicore nature, only limited sintering of the metal nanoparticles is observed at high temperatures (700 °C). In addition, the as-synthesized yolk@shell structures exhibit high and stable activity toward CO electrooxidation, thus demonstrating the applicability of our approach for the design of functional yolk@shell nanocatalysts