TY - GEN A1 - Lewerenz, Hans-Joachim A1 - Aggour, Mohammed A1 - Murrell, Chris A1 - Kanis, M. A1 - Jungblut, H. A1 - Jakubowicz, J. A1 - Cox, P. A. A1 - Campbell, S. A. A1 - Hoffmann, Patrick A1 - Schmeißer, Dieter T1 - Initial stages of structure formation on silicon electrodes investigated by photoelectron spectroscopy using synchrotron radiation and in-situ atomic force microscopy T2 - Journal of the Electrochemical Society N2 - The surface condition of electrochemically H-terminated Si is compared with the situation at the first photocurrent maximum in dilute acidic ammonium fluoride solution where the divalent dissolution converts into the four-valence process. The first high spectral-resolution photoelectron spectroscopy data using synchrotron radiation of electrochemically hydrogenated Si are presented. A combined electrochemistry/ultrahigh vacuum surface analysis system, attached to the U 49/2 beamline at the synchrotron Bessy II, is used for photoelectron spectroscopy (PES) of the electrochemically conditioned samples. We analyze the Si 2p, O 1s, and F 1s core levels. A comparison of a density functional theory calculation of the reaction sequence, proposed in the dissolution model of Gerischer and co-workers, with the PES results supports this model. The anodized sample is characterized by a residual H coverage of 0.35 monolayers evidenced by a surface core level shift, Si-OH and Si-Fx species, F-, and a higher oxidized Si species. SiO2 is not found. Even on very well H-terminated surfaces, we find residual Si-OH complexes, fluoride and water. In situ atomic force microscopy shows a roughening with a root mean square roughness parameter of 2.6 nm. %A92003 The Electrochemical Society. All rights reserved. Y1 - 2003 SN - 1945-7111 VL - 150 IS - 3 SP - E185 EP - E189 ER - TY - GEN A1 - Lewerenz, Hans-Joachim A1 - Murrell, Chris A1 - Jakubowicz, J. A1 - Aggour, Mohammed A1 - Kanis, M. A1 - Campbell, S. A. A1 - Cox, P. A. A1 - Hoffmann, Patrick A1 - Jungblut, H. A1 - Schmeißer, Dieter T1 - High Resolution Surface analysis of Si Roughenning in Dilute Ammonium Fluoride Solution T2 - Journal of Electroanalytical Chemistry N2 - The initial stages of porous Si formation on Si(111) in dilute ammonium fluoride solution are analysed by photoelectron spectroscopy using synchrotron radiation (SRPES). The PES results in the por-Si formation regime partly support a recent dissolution model. The contribution from the Si 2p surface core level shift shows that 0.35 ML of the surface is still H-terminated after interruption of the conditioning process at the first photocurrent maximum. Two signals shifted in binding energy by 0.8 and 1 eV, respectively, are attributed to reaction intermediates expected from the proposed reaction mechanism and from theoretical calculations using density functional theory (DFT). A distinct roughening is found in in-situ AFM measurements, with a calculated RMS roughness parameter of 2.6 nm. KW - Porous Si KW - transistors KW - Electropolishing KW - Photoelectron spectroscopy KW - AFM KW - Synchrotron radiation Y1 - 2003 SN - 1873-2569 VL - 540 SP - 3 EP - 6 ER - TY - GEN A1 - Brinkert, Katharina A1 - Richter, Matthias A1 - Akay, Ömer A1 - Liedtke, Janine A1 - Giersig, Michael A1 - Fountaine, Katherine T. A1 - Lewerenz, Hans-Joachim T1 - Efficient Solar Hydrogen Generation in Microgravity Environment T2 - Nature Communications N2 - Long-term space missions require extra-terrestrial production of storable, renewable energy. Hydrogen is ascribed a crucial role for transportation, electrical power and oxygen generation. We demonstrate in a series of drop tower experiments that efficient direct hydrogen production can be realized photoelectrochemically in microgravity environment, providing an alternative route to existing life support technologies for space travel. The photoelectrochemical cell consists of an integrated catalyst-functionalized semiconductor system that generates hydrogen with current densities >15 mA/cm2 in the absence of buoyancy. Conditions are described adverting the resulting formation of ion transport blocking froth layers on the photoelectrodes. The current limiting factors were overcome by controlling the micro- and nanotopography of the Rh electrocatalyst using shadow nanosphere lithography. The behaviour of the applied system in terrestrial and microgravity environment is simulated using a kinetic transport model. Differences observed for varied catalyst topography are elucidated, enabling future photoelectrode designs for use in reduced gravity environments. Y1 - 2018 U6 - https://doi.org/10.1038/s41467-018-04844-y SN - 2041-1723 IS - 9 ER - TY - GEN A1 - Brinkert, Katharina A1 - Richter, Matthias A1 - Akay, Ömer A1 - Giersig, Michael A1 - Fountaine, Katherine T. A1 - Lewerenz, Hans-Joachim T1 - Advancing semiconductor-electrocatalyst systems: application of surface transformation films and nanosphere lithography T2 - Faraday Discussions N2 - Photoelectrochemical (PEC) cells offer the possibility of carbon-neutral solar fuel production through artificial photosynthesis. The pursued design involves technologically advanced III–V semiconductor absorbers coupled via an interfacial film to an electrocatalyst layer. These systems have been prepared by in situ surface transformations in electrochemical environments. High activity nanostructured electrocatalysts are required for an efficiently operating cell, optimized in their optical and electrical properties. We demonstrate that shadow nanosphere lithography (SNL) is an auspicious tool to systematically create three-dimensional electrocatalyst nanostructures on the semiconductor photoelectrode through controlling their morphology and optical properties. First results are demonstrated by means of the photoelectrochemical production of hydrogen on p-type InP photocathodes where hitherto applied photoelectrodeposition and SNL-deposited Rh electrocatalysts are compared based on their J–V and spectroscopic behavior. We show that smaller polystyrene particle masks achieve higher defect nanostructures of rhodium on the photoelectrode which leads to a higher catalytic activity and larger short circuit currents. Structural analyses including HRSEM and the analysis of the photoelectrode surface composition by using photoelectron spectroscopy support and complement the photoelectrochemical observations. The optical performance is further compared to theoretical models of the nanostructured photoelectrodes on light scattering and propagation. KW - shadow nanosphere lithography (SNL) KW - electrocatalyst nanostructures KW - Rh electrocatalysts KW - InP photocathodes Y1 - 2018 U6 - https://doi.org/10.1039/C8FD00003D SN - 1359-6640 SN - 1364-5498 VL - 208 SP - 523 EP - 535 ER -