TY - GEN A1 - Richter, Matthias R. A1 - Cheng, Wen-Hui A1 - Crumlin, Ethan J. A1 - Drisdell, Walter S. A1 - Atwater, Harry A. A1 - Schmeißer, Dieter A1 - Lewis, Nathan S. A1 - Brunschwig, Bruce S. T1 - X‑ray Photoelectron Spectroscopy and Resonant X‑ray Spectroscopy Investigations of Interactions between Thin Metal Catalyst Films and Amorphous Titanium Dioxide Photoelectrode Protection Layers T2 - Chemistry of Materials N2 - The use of electrochemistry, X-ray photoelectron spectroscopy, and resonant X-ray spectroscopy has unlocked the paradox of interfacial hole conduction through amorphous TiO2 (a-TiO2) to deposited Ni, Ir, and Au metal catalysts. Although electrocatalysts for the oxygen-evolution reaction derived from metallic Ir and Ni have mutually similar overpotentials in alkaline media, Si/a-TiO2/Ir interfaces exhibit higher overpotentials than Si/a-TiO2/Ni interfaces. The data allow formulation of full band energy diagrams for n-Si/a-TiO2/metal interfaces for M = Ni, Ir, or Au. Although both Ni and Ir produce band bending in a-TiO2 favoring hole conduction, only Ni creates multiple states within the a-TiO2 band gap at the a-TiO2/Ni interface, which produces a quasi-metallic interface at the a-TiO2/Ni junction. Au, however, produces a flat-band interface that limits hole conduction without any new band gap states. KW - X‑ray Photoelectron Spectroscopy KW - Resonant X‑ray Spectroscopy KW - titanium oxide KW - oxygen-evolution reaction KW - protection layer KW - interface interaction Y1 - 2021 U6 - https://doi.org/10.1021/acs.chemmater.0c04043 SN - 0897-4756 SN - 1520-5002 VL - 33 IS - 4 SP - 1265 EP - 1275 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 - 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 - 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 - 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 - GEN A1 - Eriksson, Susanna K. A1 - Hahlin, Maria A1 - Axnanda, Stephanus A1 - Crumlin, Ethan J. A1 - Wilks, Regan G. A1 - Odelius, Michael A1 - Eriksson, Anna I. K. A1 - Liu, Zhi A1 - Åhlund, John A1 - Hagfeldt, Anders A1 - Starr, David E. A1 - Bär, Marcus A1 - Rensmo, Håkan A1 - Siegbahn, Hans T1 - In-situ probing of H₂O effects on a Ru-complex adsorbed on TiO₂ using ambient pressure photoelectron spectroscopy T2 - Topics in Catalysis Y1 - 2016 U6 - https://doi.org/10.1007/s11244-015-0533-3 SN - 1022-5528 SN - 1572-9028 VL - 59 IS - 5 SP - 583 EP - 590 ER -