@misc{AggourStoerkelMurrelletal., author = {Aggour, Mohammed and Stoerkel, Ulrich and Murrell, Chris and Campbell, S. A. and Jungblut, H. and Hoffmann, Patrick and Mikalo, Ricardo Pablo and Schmeißer, Dieter and Lewerenz, Hans-Joachim}, title = {Electrochemical interface modification of CuInS2 thin films}, abstract = {We studied two novel electrochemical treatments of CuInS2 solar-cell absorber films, introduced to remove the deleterious segregated CuS phase. Their influence onsurface topography, chemistry and electronic properties was investigated using in situ atomic force microscopy (AFM) and photoclectron spectroscopy, performed inpart at the U49/2 undulator beam line at BESSY II. The results are examined in order to develop an improved understanding of the chemical-electrochemical surfacetransformation processes.}, language = {en} } @misc{LewerenzAggourMurrelletal., author = {Lewerenz, Hans-Joachim and Aggour, Mohammed and Murrell, Chris and Kanis, M. and Hoffmann, Patrick and Jungblut, H. and Schmeißer, Dieter}, title = {Interface engineering of photoelectrochemically prepared Si surfaces}, abstract = {The oxide of Si(111) formed by electropolishing in dilute ammonium fluoride solution is analysed by photoelectron spectroscopy using synchrotron radiation. The oxidiclayer is about 3.1 nm thick and contains Si-F-x species as well as oxyfluorides. The oxyfluorides are found preferentially at the electropolishing layer surface. SiOHspecies are concentrated at the oxidic film/substrate interface. The full width half maximum of the Si 2p line indicates that the Si/electropolishing oxide interface issmoother than the Si/natural oxide interface.}, language = {en} } @misc{LewerenzAggourMurrelletal., author = {Lewerenz, Hans-Joachim and Aggour, Mohammed and Murrell, Chris and Kanis, M. and Jungblut, H. and Jakubowicz, J. and Cox, P. A. and Campbell, S. A. and Hoffmann, Patrick and Schmeißer, Dieter}, title = {Initial stages of structure formation on silicon electrodes investigated by photoelectron spectroscopy using synchrotron radiation and in-situ atomic force microscopy}, series = {Journal of the Electrochemical Society}, volume = {150}, journal = {Journal of the Electrochemical Society}, number = {3}, issn = {1945-7111}, pages = {E185 -- E189}, abstract = {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.}, language = {en} } @misc{LewerenzMurrellJakubowiczetal., author = {Lewerenz, Hans-Joachim and Murrell, Chris and Jakubowicz, J. and Aggour, Mohammed and Kanis, M. and Campbell, S. A. and Cox, P. A. and Hoffmann, Patrick and Jungblut, H. and Schmeißer, Dieter}, title = {High Resolution Surface analysis of Si Roughenning in Dilute Ammonium Fluoride Solution}, series = {Journal of Electroanalytical Chemistry}, volume = {540}, journal = {Journal of Electroanalytical Chemistry}, issn = {1873-2569}, pages = {3 -- 6}, abstract = {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.}, language = {en} } @inproceedings{HoffmannMikaloBatcheloretal., author = {Hoffmann, Patrick and Mikalo, Ricardo Pablo and Batchelor, David R. and Beuckert, Guido and Schmeißer, Dieter and Kittler, Martin and Ourmazd, A. and Lewerenz, Hans-Joachim}, title = {Solare Energieumwandlung in d{\"u}nnen Schichten}, language = {de} } @inproceedings{RichterLichtermanHuetal., author = {Richter, Matthias and Lichterman, Michael F. and Hu, Shu and Crumlin, Ethan J. and Axnanda, Stephanus and Favaro, Marco and Drisdell, Walter S. and Hussain, Zahid and Brunschwig, Bruce S. and Liu, Zhi and Lewis, Nathan S. and Lewerenz, Hans-Joachim}, title = {Experimental Approach for Determining Semiconductor/liquid Junction Energetics by Operando Ambient Pressure X-ray Photoelectron Spectroscopy}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, pages = {S. 409}, abstract = {The performance of a photoelectrochemical solar cell depends strongly on the electrochemical nature of the semiconductor/electrolyte junction [1]. Operando Ambient Pressure X-ray photoelectron spectroscopy investigation of semiconductor/liquid junctions provides quantitative understanding of the energy bands in these photoelectrochemical solar cells [2, 3, 4]. We demonstrate how OAP-XPS may be used to determine these relationships for semiconductor/liquid systems. The data can be analyzed to determine the energy relationship between the electronic energy bands in the semiconductor electrode and the redox levels in the solution. The major conditions for semiconductor-electrolyte contacts including accumulation, depletion, and Fermi-level pinning are observed, and the so-called flat-band energy can be determined. [1] Science 344 (2014) 1005; [2] Sci Rep 5 (2015) 9788; [3] Ener Sci 8 (2015) 2409; [4] J Electrochem Soc 162 (2016) H1}, language = {en} } @inproceedings{LichtermanRichterHuetal., author = {Lichterman, Michael F. and Richter, Matthias and Hu, Shu and Crumlin, Ethan J. and Axnanda, Stephanus and Favaro, Marco and Drisdell, Walter S. and Hussain, Zahid and Brunschwig, Bruce S. and Liu, Zhi and Lewis, Nathan S. and Lewerenz, Hans-Joachim}, title = {Probing the TiO2/Liquid Interface of a Photoelectrochemical Cell by X-Ray Photoelectron Spectroscopy}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, pages = {S. 414}, abstract = {Amorphous TiO2 coatings can stabilize semiconductor photoanodes such as Si, GaAs, and GaP that are otherwise unstable in aqueous media [1]. Using tender X-rays with their substantially increased inelastic mean free scattering length of photoelectrons and using the classical three-electrode potentiostatic arrangement allows one to follow of the influence of the applied potentials on the semiconductor electrode energetics such as band bending and band edge shifts directly [2, 3]. The observed shifts in binding energy with respect to the applied potential have directly revealed rectifying junction behavior on semiconducting samples. Accumulation, depletion and Fermi level pinning were observed. Additionally, the non-linear response of the core level binding energies to changes in the applied electrode potential has revealed the influence of defect-derived electronic states on the Galvani potential across the complete cell. [1] Science 344 (2014) 1005; [2] Sci Rep 5 (2015) 9788; [3] Ener \& Env Sci 8 (2015) 2409}, language = {en} } @inproceedings{DasTallaridaSkorupskaetal., author = {Das, Chittaranjan and Tallarida, Massimo and Skorupska, Katarzyna and Lewerenz, Hans-Joachim and Schmeißer, Dieter}, title = {An efficient Si photo cathode for a wide range of electrolyte pH values}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, abstract = {Hydrogen fuel cells, being environmental friendly to produce energy, are a technology of future. One of the efficient ways to produce hydrogen is solar driven photocatalysis using semiconducting materials as photo electrodes. The choice of electrodes is a crucial factor and is done on the basis of photo corrosion stability, light absorption efficiency, and photocarrier lifetime. P-type Si can be used as photo cathode to produce H2 by direct photocatalysis. Si cathodes can be used in acidic electrolytes to have efficient photo catalytic activity but they are unstable in alkaline electrolytes. Therefore, to use both Si electrodes in the same electrolyte, their chemical stability should be extended over a wide range of pH. To this purpose we modified the surface of a p-type Si photocathode with very thin films of TiO2 grown by atomic layer deposition (ALD). We found that the modified Si cathode shows an increased photoresponse and a lower onset potential with respect to the pristine surface and an increased stability at various pH values.}, language = {en} } @inproceedings{RichterLichtermanHuetal., author = {Richter, Matthias and Lichterman, Michael F. and Hu, Shu and Crumlin, Ethan J. and Axnanda, Stephanus and Favaro, Marco and Drisdell, Walter S. and Hussain, Zahid and Brunschwig, Bruce S. and Liu, Zhi and Lewis, Nathan S. and Lewerenz, Hans-Joachim}, title = {An Electrochemical, resonant Photoemission and Ambient Pressure-X-ray Photoelectron Spectroscopic Investigation of Si/TiO2/Ni/Electrolyte Interfaces}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, pages = {S. 414}, abstract = {Photoelectrochemical cells based on semiconductor-liquid interfaces provide a method of converting solar energy to electricity or fuels. Recently, we have demonstrated operational systems that involved stabilized semiconductor-liquid junctions [1]. The electrical and spectroscopic properties of the TiO2/Ni protection layer system have been investigated in contact with electrolyte solutions [2, 3, 4]. From the response of the photoelectron binding energies to variations in applied potential the energetics of the solid/electrolyte interface are elucidated. The degree of conductivity depended on the chemical state of the Ni on the TiO2 surface. The combinations of these techniques provide a powerful tool for the investigation of hybrid electrode/solution contacts. [1] Science 344 (2014) 1005; [2] Sci Rep 5 (2015) 9788; [3] Ener \& Env Sci 8 (2015) 2409; [4] J Electrochem Soc 162 (2016) H1}, language = {en} } @misc{BrinkertRichterAkayetal., author = {Brinkert, Katharina and Richter, Matthias and Akay, {\"O}mer and Liedtke, Janine and Giersig, Michael and Fountaine, Katherine T. and Lewerenz, Hans-Joachim}, title = {Efficient Solar Hydrogen Generation in Microgravity Environment}, series = {Nature Communications}, journal = {Nature Communications}, number = {9}, issn = {2041-1723}, doi = {10.1038/s41467-018-04844-y}, abstract = {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.}, language = {en} } @misc{BrinkertRichterAkayetal., author = {Brinkert, Katharina and Richter, Matthias and Akay, {\"O}mer and Giersig, Michael and Fountaine, Katherine T. and Lewerenz, Hans-Joachim}, title = {Advancing semiconductor-electrocatalyst systems: application of surface transformation films and nanosphere lithography}, series = {Faraday Discussions}, volume = {208}, journal = {Faraday Discussions}, issn = {1359-6640}, doi = {10.1039/C8FD00003D}, pages = {523 -- 535}, abstract = {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.}, language = {en} }