TY - CHAP A1 - Richter, Matthias A1 - Lichterman, Michael F. A1 - Hu, Shu A1 - Crumlin, Ethan J. A1 - Axnanda, Stephanus A1 - Favaro, Marco A1 - Drisdell, Walter S. A1 - Hussain, Zahid A1 - Brunschwig, Bruce S. A1 - Liu, Zhi A1 - Lewis, Nathan S. A1 - Lewerenz, Hans-Joachim T1 - Experimental Approach for Determining Semiconductor/liquid Junction Energetics by Operando Ambient Pressure X-ray Photoelectron Spectroscopy T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft N2 - 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 KW - in operando KW - ambient pressure spectroscopy KW - water splitting Y1 - 2016 UR - http://www.dpg-verhandlungen.de/year/2016/conference/regensburg/part/o/session/72/contribution/10?lang=en SP - S. 409 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Lichterman, Michael F. A1 - Richter, Matthias A1 - Hu, Shu A1 - Crumlin, Ethan J. A1 - Axnanda, Stephanus A1 - Favaro, Marco A1 - Drisdell, Walter S. A1 - Hussain, Zahid A1 - Brunschwig, Bruce S. A1 - Liu, Zhi A1 - Lewis, Nathan S. A1 - Lewerenz, Hans-Joachim T1 - Probing the TiO2/Liquid Interface of a Photoelectrochemical Cell by X-Ray Photoelectron Spectroscopy T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft N2 - 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 KW - X-Ray photoelectron spectroscopy KW - phototanodes KW - TiO2 passivation KW - water splitting Y1 - 2016 UR - http://www.dpg-verhandlungen.de/year/2016/conference/regensburg/part/o/session/82/contribution/1?lang=en SP - S. 414 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Richter, Matthias A1 - Lichterman, Michael F. A1 - Hu, Shu A1 - Crumlin, Ethan J. A1 - Axnanda, Stephanus A1 - Favaro, Marco A1 - Drisdell, Walter S. A1 - Hussain, Zahid A1 - Brunschwig, Bruce S. A1 - Liu, Zhi A1 - Lewis, Nathan S. A1 - Lewerenz, Hans-Joachim T1 - An Electrochemical, resonant Photoemission and Ambient Pressure-X-ray Photoelectron Spectroscopic Investigation of Si/TiO2/Ni/Electrolyte Interfaces T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft N2 - 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 KW - resonant photoelectron spectroscopy KW - ambient pressure spectroscopy KW - water splitting Y1 - 2016 UR - http://www.dpg-verhandlungen.de/year/2016/conference/regensburg/part/o/session/82/contribution/2?lang=en SP - S. 414 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Morales, Carlos A1 - Tschammer, Rudi A1 - Pożarowska, Emilia A1 - Kosto, Julia A1 - Villar‐Garcia, Ignacio J. A1 - Pérez‐Dieste, Virginia A1 - Favaro, Marco A1 - Starr, David E. A1 - Kapuścik, Paulina A1 - Mazur, Michał A1 - Wojcieszak, Damian A1 - Domaradzki, Jarosław A1 - Alvarado, Carlos A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Hydrogen sensing via heterolytic H₂ activation at room temperature by atomic layer deposited ceria T2 - ChemSusChem : chemistry, sustainability, energy, materials N2 - Ultrathin atomic layer deposited ceria films (<20 nm) are capable of H2 heterolytic activation at room temperature, undergoing a significant reduction regardless of the absolute pressure, as measured under in‐situ conditions by near ambient pressure X‐ray photoelectron spectroscopy. ALD‐ceria can gradually reduce as a function of H2 concentration under H2/O2 environments, especially for diluted mixtures below 10 %. At room temperature, this reduction is limited to the surface region, where the hydroxylation of the ceria surface induces a charge transfer towards the ceria matrix, reducing Ce4+ cations to Ce3+. Thus, ALD‐ceria replicates the expected sensing mechanism of metal oxides at low temperatures without using any noble metal decorating the oxide surface to enhance H2 dissociation. The intrinsic defects of the ALD deposit seem to play a crucial role since the post‐annealing process capable of healing these defects leads to decreased film reactivity. The sensing behavior was successfully demonstrated in sensor test structures by resistance changes towards low concentrations of H2 at low operating temperatures without using noble metals. These promising results call for combining ALD‐ceria with more conductive metal oxides, taking advantage of the charge transfer at the interface and thus modifying the depletion layer formed at the heterojunction. KW - Atomic Layer Deposition KW - Ceria KW - Hydrogen Sensing KW - X-Ray photoelectron spectroscopy KW - Raman spectroscopy KW - Resitive sensor Y1 - 2025 U6 - https://doi.org/10.1002/cssc.202402342 SN - 1864-5631 VL - 18 IS - 13 SP - 1 EP - 13 PB - Wiley-VCH CY - Weinheim ER -